Mesogen Compounds

ABSTRACT

The present invention relates to mesogen compounds that include a first mesogen (Mesogen-1) and a second mesogen (Mesogen-2) that are connected by a linking group (-L-), as represented by the following Formula (I): 
     
       
         
         
             
             
         
       
     
     Mesogen-1, and optionally Mesogen-2, each independently include the following terminal group, 
     
       
         
         
             
             
         
       
     
     where R is hydrogen, alkyl, or alkoxy. Mesogen-2 optionally includes a terminal group P-, which is selected from R, acrylate, methacrylate, trihalomethacrylate, oxirane, hydroxyl, carboxylic acid, and carboxylic acid ester. Mesogen-1 and Mesogen-2 together include a total of at least seven, or at least eight, cyclic groups. In some cases, Mesogen-1 and Mesengen-2 are the same. The present invention also relates to liquid crystal compositions that include such mesogen compounds, and to optical elements that include such mesogen compounds.

FIELD

The present invention relates to mesogen compounds that include firstand second mesogens that are connected by a linking group, and which areoptionally polymerizable, liquid crystal compositions that include suchmesogen compounds, and to optical elements that include such mesogencompounds.

BACKGROUND

The molecules of a liquid crystal are typically capable of aligning withone another in substantially one direction, which results in a fluidmaterial having anisotropic properties, such as with regard to optical,electromagnetic, and/or mechanical properties. A mesogen is typicallydescribed as the primary or fundamental unit (or segment or group) of aliquid crystal material that induces, and/or is induced into, structuralorder amongst and between liquid crystals (such as, other liquid crystalmaterials that are present).

Liquid crystal polymers are polymers capable of forming regions ofhighly ordered structure while in a liquid phase. Liquid crystalpolymers have a wide range of uses, including engineering plastics, andgels for liquid crystal displays (LCD' s). The structure of liquidcrystal polymers can be described as being composed of densely packedelongated polymer chains that provide self-reinforcement almost to themelting point of the polymer.

Dichroism can occur in liquid crystals, including mesogen compounds, dueto the optical anisotropy of the molecular structure, or the presence ofimpurities, or the presence of dichroic dyes and/orphotochromic-dichroic materials. As used herein, the term “dichroism”and similar terms, such as “dichroic”, means the ability to absorb oneof two orthogonal plane polarized components of radiation (includingtransmitted and/or reflected radiation) more strongly than the otherorthogonal plane polarized component. Photochromic-dichroic materialspossess both photochromic properties and dichroic properties. Aphotochromic-dichroic material, in some instances, can be described asincluding a photochromic molecule (or core, or moiety) to which iscovalently attached at least one lengthening group at least a portion ofwhich is capable of being aligned with (or by) a mesogenic material.

When used in combination with liquid crystal materials, such as mesogencompounds, the dichroic properties of photochromic-dichroic compounds,such as polarization efficiency and absorption ratio, can be enhanced.While not intending to be bound by any theory, it is believed based onthe evidence at hand, that alignment of the photochromic-dichroiccompounds with aligned mesogen compounds enhances the dichroicproperties of the photochromic-dichroic compounds, such as improvedabsorption ratio (AR) values.

The photochromic properties of photochromic-dichroic compounds can beenhanced by a chemical environment that allows the photochromic portionthereof to efficiently undergo a reversible conformational changebetween an absorbing (or colored state) and a non-absorbing (ornon-colored state). Examples of quantifiable photochromic propertiesinclude, but are not limited to: fade rate (sometimes referred to asfade half-life, T_(1/2)); change in optical density (sometimesdesignated as ΔOD); the change in optical density (ΔOD) at saturation;sensitivity (sometimes designated as ΔOD/Min); and the efficiency atwhich the photochromic compound absorbs radiation required to activatethe photochromic compound (sometimes designated as chromaticity). Thechemical environment provided by the aligned mesogen compounds, whileenhancing dichroic properties of the dichroic portion of aphotochromic-dichroic compound, can in some instances provide a chemicalenvironment that restricts or limits the efficient reversibleconformational change of the photochromic portion of thephotochromic-dichroic compound.

It would be desirable to develop new mesogen compounds that are capableof further enhancing the dichroic properties of dichroic materials, suchas photochromic-dichroic compounds. It would be further desirable thatsuch newly developed mesogen compounds maintain or enhance thephotochromic properties of photochromic-dichroic materials used inconjunction therewith.

SUMMARY

In accordance with the present invention, there is provided amesogen-containing compound represented by the following Formula (I),

With reference to Formula (I),

(A) Mesogen-1 is represented by the following Formula (II),

With reference to Formula (II),

R is selected from hydrogen, alkyl, and alkoxy; and

e′ and f′ for each occurrence for Formula (II), are independently from 0to 4, provided the sum of e′ and f′ is at least 2.

With further reference to Formula (I),

(B) Mesogen-2 is represented by Formula (II) of Mesogen-1, or thefollowing Formula (III),

With reference to Formula (III),

P is selected from R, acrylate, methacrylate, trihalomethacrylate,oxirane, hydroxyl, amino, carboxylic acid, and carboxylic acid ester;

d is 0 to 20;

S₁ independently for each d is selected from an S1-spacer unit chosenfrom: —(CH₂)—; —(O)—; —C(O)—; and —NH—, provided that when two S₁-spacerunits comprising heteroatoms are linked together, the S₁-spacer unitsare linked so that heteroatoms are not directly linked to each other;

Q₁ is a divalent group selected from the group consisting of:unsubstituted or substituted cycloaliphatic group; unsubstituted orsubstituted heterocycloaliphatic group; unsubstituted or substitutedaryl; and unsubstituted or substituted heteroaryl; wherein thecycloaliphatic group substituents, heterocycloaliphatic groupsubstituents, aryl substituents, and heteroaryl substituents are eachindependently selected from alkyl and halogen; and

e″ and f″ for each occurrence for Formula (III), are independently from0 to 6, provided the sum of e″ and f″ is at least 2.

Independently for each of Formula (II) and Formula (III),

(i) Q₂ and Q₃ for each occurrence, are independently a divalent groupselected from the group consisting of: unsubstituted or substitutedcycloaliphatic group; unsubstituted or substituted heterocycloaliphaticgroup; unsubstituted or substituted aryl; and unsubstituted orsubstituted heteroaryl; wherein the cycloaliphatic group substituents,heterocycloaliphatic group substituents, aryl substituents, andheteroaryl substituents are each independently selected from alkyl andhalogen;

(ii) S₂, S₃, and S₄ for each occurrence, are independently selected froma spacer unit chosen from: —(CH₂)—; —O—; —C(O)—; and —NH—; and

(iii) e, f, and g for each occurrence, are independently 0 to 3,provided that when two spacer units comprising heteroatoms are linkedtogether the spacer units are linked so that heteroatoms are notdirectly linked to each other.

With additional reference to Formula (I),

(C) -L- is represented by the following Formula (IV),

-(A-B)_(y)-E-  (IV)

With reference to Formula (IV),

(i) y is 1 to 30;

(ii) each A independently for each y is a divalent group selected fromthe group consisting of aliphatic group and haloaliphatic group;

(iii) each B independently for each y is a divalent group selected fromthe group consisting of: —O—; —C(O)O—; —OC(O)O—; —C(O)N(R₁)- where R₁ isH or alkyl; —NH—C(O)O—; —N(R₂)C(O)N(R₂)- where each R₂ is independentlyselected from H or alkyl;

where n is 1 to 5, and each R₃ independently for each n is selected frommethyl, ethyl, and phenyl; —Si(R₄)(R₄)- where each R₄ is independentlyselected from methyl, ethyl, and phenyl; unsubstituted or substitutedcycloaliphatic groups; unsubstituted or substituted aryl; andunsubstituted or substituted —O—(Aryl)—O—; wherein the cycloaliphaticsubstituents, the aryl substituents, and —O—(Aryl)—O— substituents areeach independently selected from alkyl, and —(S₁)_(d)-P, where S₁, d andP are each as defined with regard to Formula (III); and

(iv) E is a divalent group selected from the group consisting ofaliphatic group and haloaliphatic group.

In further accordance with the present invention, there is providedliquid crystal compositions that include the mesogen-containing compoundof the present invention, such as described with reference to Formula(I).

There is provided, in further accordance with the present invention, anoptical element that comprises: a substrate; and a layer on at least aportion of a surface of the substrate, in which the layer comprises themesogen-containing compound of the present invention, such as describedwith reference to Formula (I). The features that characterize thepresent invention are pointed out with particularity in the claims,which are annexed to and form a part of this disclosure. These and otherfeatures of the invention, its operating advantages and the specificobjects obtained by its use will be more fully understood from thefollowing detailed description in which non-limiting embodiments of theinvention are illustrated and described.

DETAILED DESCRIPTION

As used herein, the articles “a”, “an”, and “the” include pluralreferents unless otherwise expressly and unequivocally limited to onereferent.

Unless otherwise indicated, all ranges or ratios disclosed herein are tobe 20 understood to encompass any and all subranges or subratiossubsumed therein. For example, a stated range or ratio of “1 to 10”should be considered to include any and all subranges between (andinclusive of) the minimum value of 1 and the maximum value of 10; thatis, all subranges or subratios beginning with a minimum value of 1 ormore and ending with a maximum value of 10 or less, such as but notlimited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

As used herein, unless otherwise indicated, left-to-rightrepresentations of linking groups, such as divalent linking groups, areinclusive of other appropriate orientations, such as, but not limitedto, right-to-left orientations. For purposes of non-limitingillustration, the left-to-right representation of the divalent linkinggroup

or equivalently —C(O)O— or —(O)CO—, is inclusive of the right-to-leftrepresentation thereof,

or equivalently —OC(O)— or —O(O)C—.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be understood asmodified in all instances by the term “about”.

As used herein, molecular weight values of polymers, such as weightaverage molecular weights (Mw) and number average molecular weights(Mn), are determined by gel permeation chromatography using appropriatestandards, such as polystyrene standards.

As used herein, polydispersity index (PDI) values represent a ratio ofthe weight average molecular weight (Mw) to the number average molecularweight (Mn) of the polymer (i.e., Mw/Mn).

As used herein, the term “polymer” means homopolymers (such as preparedfrom a single monomer species), copolymers (such as prepared from atleast two monomer species), and graft polymers (including, but notlimited to, star polymers and comb polymer).

As used herein, the term “(meth)acrylate” and similar terms, such as“(meth)acrylic acid ester”, means methacrylates and/or acrylates. Asused herein, the term “(meth)acrylic acid” means methacrylic acid and/oracrylic acid.

As used herein, the term “photochromic” and similar terms, such as“photochromic compound”, means having an absorption spectrum for atleast visible radiation that varies in response to absorption of atleast actinic radiation. Further, as used herein, the term “photochromicmaterial” means any substance that is adapted to display photochromicproperties (such as adapted to have an absorption spectrum for at leastvisible radiation that varies in response to absorption of at leastactinic radiation) and which includes at least one photochromiccompound.

As used herein, the term “actinic radiation” means electromagneticradiation that is capable of causing a response in a material, such as,but not limited to, transforming a photochromic material from one formor state to another as discussed in further detail herein.

As used herein, the term “photochromic material” includes thermallyreversible photochromic materials and compounds and non-thermallyreversible photochromic materials and compounds. The term “thermallyreversible photochromic compounds/materials” as used herein meanscompounds/materials capable of converting from a first state (such as a“clear state”) to a second state (such as a “colored state”) in responseto actinic radiation, and reverting back to the first state in responseto thermal energy. The term “non-thermally reversible photochromiccompounds/materials” as used herein means compounds/materials capable ofconverting from a first state (such as a “clear state”) to a secondstate (such as a “colored state”) in response to actinic radiation, andreverting back to the first state in response to actinic radiation ofsubstantially the same wavelength(s) as the absorption(s) of the coloredstate.

As used herein, to modify the term “state”, the terms “first” and“second” are not intended to refer to any particular order orchronology, but instead refer to two different conditions or properties.For purposes of non-limiting illustration, the first state and thesecond state of a photochromic compound can differ with respect to atleast one optical property, such as but not limited to the absorption ofvisible and/or UV radiation. Thus, according to various non-limitingembodiments disclosed herein, the photochromic compounds used inconjunction with the present invention can have a different absorptionspectrum in each of the first and second state. For example, while notlimiting herein, a photochromic compound used in conjunction with thepresent invention can be clear in the first state and colored in thesecond state. Alternatively, a photochromic compound used in conjunctionwith the present invention can have a first color in the first state anda second color in the second state. Additionally, aphotochromic-dichroic compound used in conjunction with the presentinvention can have a first alignment in a first state, and a secondalignment in a second state, in which one of the first alignment andsecond alignment is substantially non-aligned.

As used herein, the term “optical” means pertaining to or associatedwith light and/or vision. For example, according to various non-limitingembodiments disclosed herein, the optical article or element or devicecan be chosen from ophthalmic articles, elements and devices, displayarticles, elements and devices, windows, mirrors, and active and passiveliquid crystal cell articles, elements and devices.

As used herein, the term “ophthalmic” means pertaining to or associatedwith the eye and vision. Non-limiting examples of ophthalmic articles orelements include corrective and non-corrective lenses, including singlevision or multi-vision lenses, which can be either segmented ornon-segmented multi-vision lenses (such as, but not limited to, bifocallenses, trifocal lenses, and progressive lenses), as well as otherelements used to correct, protect, or enhance (cosmetically orotherwise) vision, including, without limitation, contact lenses,intraocular lenses, magnifying lenses, and protective lenses or visors.

As used herein, the term “display” means the visible or machine-readablerepresentation of information in words, numbers, symbols, designs ordrawings. Non-limiting examples of display elements include screens,monitors, and security elements, such as security marks.

As used herein, the term “window” means an aperture adapted to permitthe transmission of radiation there-through. Non-limiting examples ofwindows include automotive, marine, rail, and aircraft transparencies;windshields; filters; shutters; and optical switches.

As used herein, the term “mirror” means a surface that specularlyreflects a large fraction of incident light.

As used herein, the term “liquid crystal cell” refers to a structurecontaining a liquid crystal material that is capable of being ordered. Anon-limiting example of a liquid crystal cell element is a liquidcrystal display.

As used herein, the terms “formed over”, “deposited over”, “providedover”, “applied over”, “residing over”, or “positioned over”, meanformed, deposited, provided, applied, residing, or positioned on but notnecessarily in direct (or abutting) contact with the underlying element,or surface of the underlying element. For example, a layer “positionedover” a substrate does not preclude the presence of one or more otherlayers, coatings, or films of the same or different composition locatedbetween the positioned or formed layer and the substrate.

All documents, such as but not limited to issued patents and patentapplications, referred to herein, and unless otherwise indicated, are tobe considered to be “incorporated by reference” in their entirety.

As used herein, the term “aliphatic” and related terms, such as“aliphatic group(s)”, means non-cyclic and non-aromatic hydrocarbongroups, which include at least one carbon atom, such as 1 to 20 carbonatoms, such as C₁-C₂₀ aliphatic groups, or C₁-C₁₀ aliphatic groups, orC₁-C₆ aliphatic groups; can be linear or branched; optionally includeone or more interior and/or terminal alkene (or alkenyl) groups; andoptionally include one or more interior and/or terminal alkyne (oralkynyl) groups. When including two or more alkene groups, the alkenegroups of an aliphatic group can be conjugated and/or non-conjugated.When including two or more alkyne groups, the alkyne groups of analiphatic group can be conjugated and/or non-conjugated. When includingat least one alkene group and at least one alkyne group, the alkene andalkyne groups of the aliphatic group can be conjugated and/ornon-conjugated relative to each other.

Examples of aliphatic groups include, but are not limited to, alkylgroups. As used herein, the term “alkyl” and related terms, such as“alkyl group(s)”, means groups which include at least one carbon atom,such as 1 to 20 carbon atoms, such as C₁-C₂₀ alkyl groups, or C₁-C₁₀alkyl groups, or C₁-C₆ alkyl groups; are linear or branched; and aresaturated (and correspondingly are free of alkene groups and alkynegroups). Examples of alkyl groups include, but are not limited to,methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl,t-butyl, linear or branched pentyl, linear or branched hexyl, linear orbranched heptyl, linear or branched octyl, linear or branched nonyl,linear or branched decyl, linear or branched undencyl, linear orbranched dodecyl, linear or branched tridecyl, linear or branchedtetradecyl, linear or branched pentadecyl, linear or branched hexadecyl,linear or branched heptadecyl, linear or branched octadecyl, linear orbranched nonadecyl, and linear or branched eicosanyl.

As used herein, recitations of “linear or branched” groups, such as, butnot limited to, linear or branched alkyl, are herein understood toinclude, for purposes of no-limiting illustration, a methylene group ora methyl group; groups that are linear, such as linear C₂-C₂₀ alkylgroups; and groups that are appropriately branched, such as, but notlimited to, branched C₃-C₂₀ alkyl groups.

Examples of aliphatic groups include, but are not limited to, alkenylgroups. As used herein, the term “alkenyl” and related terms, such as“alkenyl groups”, means groups which include at least two carbon atoms,such as 2 to 20 carbon atoms, such as C₂-C₂₀ alkenyl groups, or C₂-C₁₀alkenyl groups, or C2-C6 alkenyl groups; are linear or branched; andinclude one or more interior and/or terminal alkene (or alkenyl) groups.Examples of alkenyl groups include, but are not limited to, thoseexamples of linear or branched alkyl groups recited previously herein,which have at least two carbon atoms and at least one alkene (oralkenyl) group, such as, but not limited to, ethenyl, linear or branchedpropenyl, linear or branched butenyl, linear or branched pentenyl,linear or branched hexencyl, etc.

Examples of aliphatic groups include, but are not limited to, alkynylgroups. As used herein, the term “alkynyl” and related terms, such as“alkynyl group(s)”, means groups which include at least two carbonatoms, such as 2 to 20 carbon atoms, such as C₂-C₂₀ alkynyl groups, orC₂-C₁₀ alkynyl groups, or C₂-C₆ alkynyl groups; are linear or branched;and include one or more interior and/or terminal alkyne (or alkynyl)groups. Examples of alkynyl groups include, but are not limited to,those examples of linear or branched alkyl groups recited previouslyherein, which have at least two carbon atoms and at least one alkyne (oralkynyl) group, such as, but not limited to, ethynyl, propynyl, linearor branched butynyl, linear or branched pentynyl, linear or branchedhexynyl, etc.

As used herein, the term “haloaliphatic” and related terms, such as“haloaliphatic group(s)”, means non-cyclic and non-aromatic hydrocarbongroups, which include at least one carbon atom, such as 1 to 20 carbonatoms, such as C₁-C₂₀ haloaliphatic groups, or C₁-C₁₀ haloaliphaticgroups, or C₁-C₆ haloaliphatic groups; include at least one halo groupselected from fluoro (F), chloro (Cl), bromo (Br), and/or iodo (I); arelinear or branched; optionally include one or more interior and/orterminal alkene groups; and optionally include one or more interiorand/or terminal alkyne groups. When including two or more alkene groups,the alkene groups of an haloaliphatic group can be conjugated and/ornon-conjugated. When including two or more alkyne groups, the alkynegroups of an haloaliphatic group can be conjugated and/ornon-conjugated. When including at least one alkene group and at leastone alkyne group, the alkene and alkyne groups of the haloaliphaticgroup can be conjugated and/or non-conjugated relative to each other. Atleast one available hydrogen of, and up to all available hydrogens of, ahaloaliphatic group can be replaced with a halo group, such as selectedfrom fluoro (F), chloro (Cl), bromo (Br), and/or iodo (I).Correspondingly, as used herein, the term “haloaliphatic” includes, butis not limited to, “perhaloaliphatic” and related terms, such as“perhaloaliphatic group(s)”.

Examples of haloaliphatic groups include, but are not limited to,haloalkyl groups. As used herein, the term “haloalkyl” and relatedterms, such as “haloalkyl group(s)”, means groups which include at leastone carbon atom, such as 1 to 20 carbon atoms, such as C1-C20 haloalkyl,or C₁-C₁₀ haloalkyl, or C₁-C₆ haloalkyl; are linear or branched; includeat least one halo group, such as selected from fluoro (F), chloro (Cl),bromo (Br), and/or iodo (I); and are saturated (and correspondingly arefree of alkene groups and alkyne groups). At least one availablehydrogen of, and up to all available hydrogens of, a haloalkyl group canbe replaced with a halo group, such as selected from fluoro (F), chloro(Cl), bromo (Br), and/or iodo (I). Correspondingly, as used herein, theterm “haloalkyl” includes, but is not limited to, “perhaloalkyl” andrelated terms, such as “perhaloalkyl group(s)”. Examples of haloalkylgroups include, but are not limited to, those examples of linear orbranched alkyl groups recited above, which include at least one halogroup, such as, but not limited to, halomethyl, haloethyl, linear orbranched halopropyl, linear or branched halobutyl, linear or branchedhalopentyl, linear or branched halohexyl, etc., each independentlyincluding at least one halo group.

Examples of haloaliphatic groups include, but are not limited to,haloalkenyl groups. As used herein, the term “haloalkenyl” and relatedterms, such as “haloalkenyl group(s)”, means groups which include atleast two carbon atoms, such as 2 to 20 carbon atoms, such as C₂-C₂₀haloalkenyl, or C₂-C₁₀ io haloalkenyl, or C₂-C₆ haloalkenyl; are linearor branched; include at least one halo group, such as selected fromfluoro (F), chloro (Cl), bromo (Br), and/or iodo (I); and include one ormore interior and/or terminal alkene (or alkenyl) groups. Examples ofhaloalkenyl groups include, but are not limited to, those examples oflinear or branched alkyl groups recited above, which have at least twocarbon atoms, at least one alkene (or alkenyl) group, and at least onehalo group, such as, but not limited to, haloethenyl, linear or branchedhalopropenyl, linear or branched halobutenyl, linear or branchedhalopentenyl, linear or branched halohexenyl, etc., each independentlyincluding at least one halo group.

Examples of haloaliphatic groups include, but are not limited to,haloalkynyl

groups. As used herein, the term “haloalkynyl” and related terms, suchas “haloalkynyl group(s)”, means groups which include at least twocarbon atoms, such as 2 to 20 carbon atoms, such as C₂-C₂₀ haloalkynyl,or C₂-C₁₀ haloalkynyl, or C₂-C₆ haloalkynyl; are linear or branched;include at least one halo group (or halogen group), such as selectedfrom fluoro (F), chloro (Cl), bromo (Br), and/or iodo (I); and includeone or more interior and/or terminal alkyne (or alkynyl) groups.

Examples of haloalkynyl groups include, but are not limited to, thoseexamples of linear or branched alkyl groups recited above, which have atleast two carbon atoms, at least one alkyne (or alkynyl) group, and atleast one halo group, such as, but not limited to, haloethynyl,halopropynyl, linear or branched halobutynyl, linear or branchedhalopentynyl, linear or branched halohexynyl, etc., each independentlyincluding at least one halo group.

As used herein, the term “cycloaliphatic” and related terms, such as“cycloaliphatic group(s)”, means cyclic and non-aromatic hydrocarbongroups, which include at least three carbon atoms, such as 3 to 20carbon atoms, such as C₃-C₂₀ cycloaliphatic groups, or C3-C₁₀cycloaliphatic groups, or C₃-C₈ cycloaliphatic groups; optionallyinclude at least one unsaturated group selected from alkene and/oralkyne; and optionally include two or more fused cycloaliphatic rings.

Examples of cycloaliphatic groups include, but are not limited to,cycloalkyl groups. As used herein, the term “cycloalkyl” and relatedterms, such as “cycloalkyl group(s)”, means groups which include atleast three carbon atoms, such as 3 to 20 carbon atoms, such as C₃-C₂₀cycloalkyl groups, or C₃-C₁₀ cycloalkyl groups, or C₃-C₈ cycloalkylgroups; optionally include at least one unsaturated group selected fromalkene and/or alkyne; and optionally include two or more fusedcycloalkyl rings. Examples of cycloalkyl groups include, but are notlimited to, cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl;cycloheptyl; cyclooctyl; cyclononyl; cyclodecyl; cycloundecyl;cyclododecyl; bicyclo [2.2.1] heptanyl; decahydronaphthalenyl;tetradecahydroanthracenyl; tetradecahydrophenanthrenyl; anddodecahydro-1H-phenalenyl.

As used herein, the term “heterocycloaliphatic” and related terms, suchas “heterocycloaliphatic group(s)”, means cyclic and non-aromaticgroups, which include at least two carbon atoms, such as 2 to 20 carbonatoms, such as C₂- C₂₀ heterocycloaliphatic groups, or C₂-C₁₀heterocycloaliphatic groups, or C₂-C₈ heterocycloaliphatic groups; andwhich have at least one hetero atom in the cyclic ring, such as, but notlimited to, O, S, N, P, and combinations thereof; optionally include atleast one unsaturated group selected from alkene and/or alkyne; andoptionally include two or more fused non-aromatic cyclic rings, at leastone of which is a fused heterocycloaliphatic ring.

Examples of heterocycloaliphatic groups include, but are not limited to,heterocycloalkyl groups. As used herein, the term “heterocycloalkyl” andrelated terms, such as “heterocycloalkyl group(s)”, means groups whichinclude at least two carbon atoms, such as 2 to carbon atoms, such asC₂-C₂₀ heterocycloalkyl groups, or C₂-C₁₀ heterocycloalkyl groups, orC₂-C₈ heterocycloalkyl groups; and which have at least one hetero atomin the cyclic ring, such as, but not limited to, O, S, N, P, andcombinations thereof; optionally include at least one unsaturated groupselected from alkene and/or alkyne; and optionally include two or morefused non-aromatic cyclic rings, at least one of which is a fusedheterocycloalkyl ring. Examples of heterocycloalkyl groups include, butare not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl,piperidinyl, piperazinyl, morpholinyl, 7-oxabicyclo[2.2.1]heptanyl,octahydrocyclopenta[b]pyranyl, and octahydro-1H-isochromenyl.

As used herein, the term “aryl” and related terms, such as “arylgroup(s)”, means cyclic aromatic hydrocarbon groups, which include atleast 5 carbon atoms, such as C₅-C₂₀ aryl groups, or C₅-C₁₄ aryl groups;and optionally include at least two fused aromatic rings. Examples ofaryl groups include, but are not limited to, phenyl, naphthalenyl,anthracenyl, phenanthrenyl, triphenylenyl, 9,10-dihydroanthracenyl,9,10-dihydrophenanthrenyl, and triptycenyl.

As used herein, the term “heteroaryl” and related terms, such as“heteroaryl group(s)”, means cyclic aromatic hydrocarbon groups, whichinclude at least 3 carbon atoms, such as C₃-C₂₀ heteroaryl groups, orC₅-C₁₄ heteroaryl groups; at least one heteroatom in the aromatic ring,such as —O—, —N—, and/or —S—; and optionally include at least two fusedaromatic rings, at least one of which is a fused heteroaryl ring.Examples of hetroaryl groups include, but are not limited to, pyrazolyl,imidazolyl, triazinyl, furanyl, thiophenyl, pyranyl, pyridinyl,isoquinolinyl, and pyrimidinyl.

As used herein, the term “alkoxy” and related terms, such as “alkoxygroup(s)”, means an alkyl group which includes at least one carbon atom,such as 1 to 20 carbon atoms, such as C₁-C₂₀ alkoxy, or C₁-C₁₀ alkoxy,or C₁-C₆ alkoxy. Examples of alkoxy groups include, but are not limitedto, those examples of alkyl groups recited previously herein, whichinclude a terminal divalent oxygen linkage or group (or terminal etherlinkage or group), such as, but not limited to, methoxy (CH₃—O—), ethoxy(CH₃CH₂—O—), n-propoxy (CH₃CH₂CH₂—O—), iso-propoxy, linear or branchedbutoxy, linear or branched pentoxy, linear or branched hexoxy, etc.

As used herein, the term “amino” and related terms, such as “aminogroup”, includes groups represented by —N(R¹¹)(R¹²), where R¹¹ and R¹²are each independently selected, for example, from hydrogen, aliphaticgroups, cycloaliphatic groups, heterocycloaliphatic groups, aryl groups,and heteroaryl groups.

As used herein, the term “halogen” and related terms, such as “halogengroup(s)” and/or “halo group(s)”, means a single bonded halogen atom,such as selected from fluoro (F), chloro (Cl), bromo (Br), and/or iodo(I).

As used herein, and unless otherwise explicitly stated, the term“hydrogen” and related terms, such as “hydrogen group(s)”, means asingle bonded hydrogen (—H).

With reference to Formula (II), and with some embodiments, R is selectedfrom hydrogen, alkyl, and alkoxy. With further reference to Formula(II), and in accordance with some further embodiments, R is selectedfrom hydrogen and alkyl. The alkyl and alkoxy groups from which R ofFormula (II) can be selected include, but are not limited to, thoseclasses and examples of alkyl and alkoxy groups described previouslyherein. With some embodiments, R of Formula (II) is selected fromhydrogen, methyl, ethyl, n-propyl, i-propyl, linear or branched butyl,linear or branched pentyl, linear or branched hexyl, methoxy, ethoxy,n-propoxy, i-propoxy, linear or branched butoxy, linear or branchedpentoxy, and linear or branched hexoxy.

With some embodiments, e′ and f′ for each occurrence for Formula (II)are independently from 0 to 4 (such as 0, 1, 2, 3, or 4, andcombinations thereof); provided the sum of e′ and f′ is at least 2, suchas from 2 to 8, or 2 to 5, or 2 to 4.

With reference to Formula (III), and in accordance with someembodiments, P is selected from R, as described with regard to Formula(II); acrylate (CH₂═CHC(O)O—), methacrylate (CH₂═C(CH₃)C(O)O—);trihalomethacrylate (CH₂═C(CX₃)C(O)O- where each X independently is ahalogen or halo group); oxirane

hydroxyl (—OH); amino; carboxylic acid (-C(0)OH); and carboxylic acidester (-C(0)OR', where R′ is selected from aliphatic group,cycloaliphatic group, aryl, and heteroaryl). Examples oftrihalomethacrylate from which P can be selected include, but are notlimited to, trifluoromethacrylate and trichloromethacrylate.

In accordance with some embodiments, and with reference to Formula(III), subscript d is 0 to 20, or 0 to 15, or 0 to 12, or 0 to 10, or 0to 8, or 0 to 5.

With further reference to Formula (III), S i independently for each d isselected from an S₁-spacer unit chosen from —(CH₂)—; —O—; —C(O)—; and—NH—, provided that when two S₁-spacer units including heteroatoms arelinked together, the S₁-spacer units are linked so that heteroatoms arenot directly linked to each other. Adjacent S₁-spacer units can togetherform various divalent linkages, such as, but not limited to, alkyllinkages; ether linkages; ester (or carboxylate) linkages, —O—C(O)-and/or —C(O)—O—; carbonate linkages,—O—C(O)—O—; amide linkages,—NH—C(O)- and/or —C(O)—NH—; urea linkages, —NH—C(O)—NH—; carbamatelinkages, —O—C(O)—NH- and/or —NH—C(O)—O—; dione linkages, —C(O)—C(O)—;and combinations thereof, provided that the S₁-spacer units are linkedso that heteroatoms are not directly linked to each other. With someembodiments, S₁-spacer units being linked so that heteroatoms are notdirectly linked to each other, means that —(S₁)_(d)- is free of: —O-bonded directly to —O—; —NH- bonded directly to —NH—; and —O- and —NH-bonded directly to each other.

With some embodiments, e″ and f″ for each occurrence for Formula (III),are independently from 0 to 6 (such as 0, 1, 2, 3, 4, 5, or 6, andcombinations thereof), provided the sum of e″ and f″ is at least 2, suchas from 2 to 10, or 2 to 5, or 2 to 4.

Independently for each of Formula (II) and Formula (III), and inaccordance with some embodiments, S₂, S₃, and S₄ for each occurrence areindependently selected from a spacer unit chosen from —(CH₂)—, —O—,—C(O)—, and —NH—; subscripts e, f, and g for each occurrence areindependently 0 to 3 (such as 0, 1, 2, or 3); provided that when twospacer units including heteroatoms are linked together the spacer unitsare linked so that heteroatoms are not directly linked to each other.Adjacent spacer units from which each of S₂, S₃, and S₄ are eachindependently selected can together form various linkages (such as, butnot limited to, divalent linkages), such as, but not limited to, alkyllinkages; ether linkages; ester (or carboxylate) linkages, —O—C(O)-and/or —C(O)—O—; carbonate linkages,—O—C(O)—O—; amide linkages,—NH—C(O)- and/or —C(O)—NH—; urea linkages, —NH—C(O)—NH—; carbamatelinkages, —O—C(O)—NH- and/or —NH—C(O)—O—; dione linkages, —C(O)—C(O)—;and combinations thereof, provided that the spacer units are linked sothat heteroatoms are not directly linked to each other. With someembodiments, spacer units (from which each of S₂, S₃, and S₄ are eachindependently selected) being linked so that heteroatoms are notdirectly linked to each other, means that such combinations of adjacentspacer units are free of —O- bonded directly to —O—; —NH- bondeddirectly to —NH—; and —O- and —NH- bonded directly to each other.

With reference to Formula (III) and in accordance with some embodimentsof the present invention, Q₁ is a divalent group selected fromunsubstituted or substituted cycloalkyl; unsubstituted or substitutedphenyl; unsubstituted or substituted naphthyl; and unsubstituted orsubstituted triptycenyl; in which the cycloalkyl substituents, phenylsubstituents, naphthyl substituents, and triptycenyl substituents, areeach independently selected from alkyl and halogen, where the alkylgroups and halogen groups are each selected from those classes andexamples as described previously herein. With further embodiments, andindependently for each of Formula (II) and Formula (III), Q₂ and Q₃ foreach occurrence are independently a divalent group selected fromunsubstituted or substituted cycloalkyl; unsubstituted or substitutedphenyl; unsubstituted or substituted naphthyl; and unsubstituted orsubstituted triptycenyl; in which the cycloalkyl substituents, phenylsubstituents, naphthyl substituents, and triptycenyl substituents, areeach independently selected from alkyl and halogen, where the alkylgroups and halogen groups are each selected from those classes andexamples as described previously herein.

With reference to Formula (III) and in accordance with some additionalembodiments of the present invention, Q₁ is a divalent group selectedfrom unsubstituted or substituted 1,4-cyclohexyl; unsubstituted orsubstituted 1,4-phenyl; unsubstituted or substituted 1,5-naphthyl;unsubstituted or substituted 2,6-naphthyl; unsubstituted or substituted1,8-naphthyl; and unsubstituted or substituted 1,4-triptycenyl, in whichthe 1,4-cyclohexyl substituents, 1,4-phenyl substituents, 1,5-naphthylsubstituents, 2,6-naphthyl substituents, 1,8-naphthyl substituents, and1,4-triptycenyl substituents, are each independently selected from alkyland halogen, where the alkyl groups and halogen groups are each selectedfrom those classes and examples as described previously herein. Withsome further embodiments, and independently for each of Formula (II) andFormula (III), Q₂ and Q₃ for each occurrence are independently adivalent group selected from the group consisting of unsubstituted orsubstituted 1,4-cyclohexyl; unsubstituted or substituted 1,4-phenyl;unsubstituted or substituted 1,5-naphthyl; unsubstituted or substituted2,6-naphthyl; unsubstituted or substituted 1,8-naphthyl; andunsubstituted or substituted 1,4-triptycenyl, wherein the 1,4-cycloalkylsubstituents, 1,4-phenyl substituents, 1,5-naphthyl substituents,2,6-naphthyl substituents, 1,8-naphthyl substituents, and1,4-triptycenyl substituents, are each independently selected from alkyland halogen, where the alkyl groups and halogen groups are each selectedfrom those classes and examples as described previously herein.

With some embodiments of the mesogen-containing compounds of the presentinvention, and with reference to Formula (I), Mesogen-2 is representedby Formula (II) of Mesogen-1.

With some further embodiments of the mesogen-containing compounds of thepresent invention, and with reference to Formula (I), Mesogen-2 isrepresented by Formula (II) of Mesogen-1, and Mesogen-1 and Mesogen-2are the same.

With reference to Formula (I), and with some embodiments, -L- isrepresented by Formula (IV) provided previously herein in which y isfrom 1 to 30, or 2 to 20; and in which each A independently for each yis a divalent group selected from an aliphatic group and a haloaliphaticgroup. With some further embodiments, and with reference to Formula (I),-L- is represented by Formula (IV) provided previously herein, in whicheach A independently for each y is a divalent group selected from alkylgroups and haloalkyl groups, in which the alkyl groups and haloalkylgroups are each selected from those classes and examples of alkyl groupsand haloalkyl groups described previously herein.

With further reference to Formula (IV), and in accordance with somefurther embodiments, B independently for each y is a divalent groupselected from —O—; —C(O)O—; —OC(O)O—; —C(O)N(R₁)- where R₁ is H oralkyl; —NH—C(O)O—; —N(R₂)C(O)N(R₂)- where each R₂ is independentlyselected from H or alkyl;

where n is 1 to 5, and each R₃ independently for each n is selected frommethyl, ethyl, and phenyl; —Si(R₄)(R₄)- where each R₄ is independentlyselected from methyl, ethyl, and phenyl; unsubstituted or substitutedcycloalkyl (such as, but not limited to, cyclohexyl); unsubstituted orsubstituted phenyl; and unsubstituted or substituted —O—(Phenyl)—O—; inwhich the cycloalkyl substituents, the phenyl substituents, and—O—(Phenyl)—O- substituents are each independently selected from alkyl,and —(S₁)_(d)-P, where S₁, d and P are each as described with regard toFormula (III). The alkyl groups from which each of R₂, R₃, and R_(4,)and the various substituents can be independently selected include, butare not limited to, those classes and examples of alkyl groups describedpreviously herein.

With further reference to Formula (IV), E is a divalent group selectedfrom the group consisting of aliphatic groups and haloaliphatic groups.With additional reference to Formula (IV), and with some embodiments, Eis a divalent group selected from alkyl groups and haloalkyl groups, inwhich the alkyl groups and haloalkyl groups are each selected from thoseclasses and examples of alkyl groups and haloalkyl groups describedpreviously herein.

With some embodiments, and with reference to Formula (IV), no B is adivalent group selected from, unsubstituted or substitutedcycloaliphatic groups, unsubstituted or substituted aryl, andunsubstituted or substituted —O—(Aryl)—O—; or only one B is a divalentgroup selected from, unsubstituted or substituted cycloaliphatic groups,unsubstituted or substituted aryl, and unsubstituted or substituted—O—(Aryl)—O—.

With some further embodiments, and with further reference to Formula(IV), no B is a divalent group selected from, unsubstituted orsubstituted cycloalkyl (such as, but not limited to, unsubstituted orsubstituted cyclohexyl), unsubstituted or substituted phenyl,unsubstituted or substituted naphthyl, and unsubstituted or substituted—O—(Phenyl)—O—; or only one B is a divalent group selected from,unsubstituted or substituted cycloalkyl (such as, but not limited to,unsubstituted or substituted cyclohexyl), unsubstituted or substitutedphenyl, unsubstituted or substituted naphthyl, and unsubstituted orsubstituted —O—(Phenyl)—O—.

As used herein, recitations of “—O—(Aryl)—O—” means an aryl group thatincludes two —O- linking groups, and which can be represented by thefollowing Formula (V),

With reference to Formula (V), and correspondingly —O—(Aryl)—O—, thearyl group (or portion, or ring) can be selected from those classes andexamples of aryl groups as described previously herein.

As used herein, recitations of —O—(Phenyl)—O- means a phenyl group thatincludes two —O- linking groups, and which can be represented by thefollowing Formula (VI),

With reference to Formula (I), and in accordance with some embodiments,-L- includes at least 20 bonds, such as 20 to 200 bonds (or 30 to 200bonds), or 20 to 150 bonds (or 30 to 150 bonds), or 30 to 140 bonds (or40 to 140 bonds), or 30 to 130 bonds (or to 130 bonds), or 40 to 120bonds (or 50 to 120 bonds), or 50 to 110 bonds, where each bond isindependently selected from a single bond, a double bond, and a triplebond.

With some embodiments, the linking group -L-, that links Mesogen-1 andMesogen-2 together, is itself free of mesogen properties (the linkinggroup -L- is non-mesogenic).

In accordance with some embodiments, -L- of Formula (I) is selected fromthe following Formulas L(1) through L(23), including combinations of twoor more thereof:

With reference to Formulas L(1) through L(23), each t, each u, each v,and each w,

for each occurrence, are each independently from 1 to 20.

The present invention relates to a liquid crystal composition thatincludes the mesogen-containing compound(s) of the present invention,such as described with reference to Formula (I). Liquid crystalcompositions according to the present invention, in some embodiments, inaddition to at least one compound represented by Formula I, can furtherinclude at least one of a photochromic compound, a dichroic compound,and/or a photochromic-dichroic compound.

Classes of photochromic compounds that can be present in the liquidcrystal compositions of the present invention include, but are notlimited to, indeno-fused naphthopyrans, naphtho [1,2-b]pyrans, naphtho[2,1-b]pyrans, spirofluoroeno [1,2-b]pyrans, phenanthropyrans,quinolinopyrans, fluoroanthenopyrans, spiropyrans, benzoxazines,naphthoxazines, spiro(indoline)naphthoxazines,spiro(indoline)pyridobenzoxazines, spiro(indoline)fluoranthenoxazines,spiro(indoline)quinoxazines, fulgides, fulgimides, diarylethenes,diarylalkylethenes, diarylalkenylethenes, non-thermally reversiblephotochromic compounds, and mixtures thereof.

Photochromic-dichroic compounds that can be present in the liquidcrystal compositions of the present invention typically include at leastone photochromic moiety; and at least one covalently bonded lengtheninggroup, which can include at least one mesogenic segment. With someembodiments, each photochromic moiety of the photochromic-dichroiccompound is selected from indeno-fused naphthopyrans, naphtho[1,2-b]pyrans , naphtho [2,1-b]pyrans, spirofluoroeno [1,2-b]pyrans ,phenanthropyrans, quinolinopyrans, fluoroanthenopyrans, spiropyrans,benzoxazines, naphthoxazines, spiro(indoline)naphthoxazines,spiro(indoline)pyridobenzoxazines, spiro(indoline)fluoranthenoxazines ,spiro(indoline)quinoxazines, fulgides, fulgimides, diarylethenes,diarylalkylethenes, diarylalkenylethenes, non-thermally reversiblephotochromic compounds, and combinations thereof.

Classes and examples of lengthening groups of the photochromic-dichroiccompounds that can be included in the liquid crystal compositions of thepresent invention include, but are not limited to, those described atcolumns 37-51 of U.S. Pat. No. 9,334,439 B2, which disclosure isincorporated herein by reference.

Liquid crystal compositions according to the present invention canoptionally further include at least one additive. Examples of suchoptional additives include, but are not limited to, liquid crystalmaterials, liquid crystal property control additives, non-linear opticalmaterials, dyes (e.g., static dyes), dichroic dyes, blue light blocking(or filtering) agents, alignment promoters, kinetic enhancers,photoinitiators, thermal initiators, surfactants, polymerizationinhibitors, solvents, light stabilizers, thermal stabilizers, moldrelease agents, rheology control agents, gelators, leveling agents, freeradical scavengers, coupling agents, tilt control additives, block ornon-block polymeric materials, and/or adhesion promoters. Classes andexamples of blue light blocking (or filtering) agents include, but arenot limited to, those described in U.S. Pat. No. 9,683,102 B2 and US2015/0234208 A1, the pertinent portions of which are incorporated hereinby reference.

Classes of solvents that can be included in the liquid crystalcompositions of the present invention include, with some embodiments,water, organic solvents, and combinations thereof. Classes of organicsolvents that can be present in the liquid crystal compositions of

the present invention include, but are not limited to, alcohols, such asmethanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butylalcohol, tert-butyl alcohol, iso-butyl alcohol, benzyl alcohol, furfurylalcohol, and tetrahydrofurfuryl alcohol; ketones or ketoalcohols, suchas acetone, methyl ethyl ketone, and diacetone alcohol; ethers, such asdimethyl ether and methyl ethyl ether; cyclic ethers, such astetrahydrofuran, and dioxane; esters, such as ethyl acetate,2-butoxyethylacetate, ethyl lactate, ethylene carbonate, and propylenecarbonate, in particular 1,2-propanediol cyclic carbonate; hydroxyfunctional ethers of alkylene glycols, such as butyl 2-hydroxyethylether, methyl 2-hydroxypropyl ether, and phenyl 2-hydroxypropyl ether;nitrogen containing cyclic compounds, such as pyrrolidone,N-methyl-2-pyrrolidone, 1-butylpyrrolidin-2-one, and1,3-dimethyl-2-imidazolidinone; sulfur containing compounds, such asdimethyl sulfoxide and tetramethylene sulfone; aromatic compounds, suchas toluene, xylene, anisole, and butyl benzoate; and mixtures ofaromatic compounds, such as, but not limited to, Aromatic 100 Fluid,which is a commercially available mixture of C₉-C₁₀ dialkyl- andtrialkyl-benzenes, or Aromatic 150 Fluid, which is a commerciallyavailable mixture of C₉-C₁₁ alkyl benzenes.

Examples of dichroic dyes that can be included in the liquid crystalcompositions

of the present invention include, but are not limited to, azomethines,indigoids, thioindigoids, merocyanines, indans, quinophthalonic dyes,perylenes, phthaloperines, triphenodioxazines, indoloquinoxalines,imidazo-triazines, tetrazines, azo and (poly)azo dyes, benzoquinones,naphthoquinones, anthroquinone and (poly)anthroquinones,anthropyrimidinones, iodine, iodates, or combinations of two or morethereof.

In accordance with the present invention, there is further provided anoptical element that includes a substrate; and a layer on (or over) atleast a portion of a surface of the substrate, in which the layerincludes at least one mesogen-containing compound according to thepresent invention.

The substrate of the optical element, with some embodiments, is anoptical

substrate, which can include organic materials (such as organicpolymers), inorganic materials, or combinations thereof (for example,composite materials). Examples of substrates that can be included in theoptical elements of the present invention include, but are not limitedto, those described at column 35, line 5 through column 36, line 57 ofU.S. Pat. No. 8,628,685 B2, which disclosure is incorporated herein byreference.

The layer(s) provided over the substrate of the optical elements of thepresent invention include, with some embodiments, an organic matrix,such as an organic polymer matrix, which can be a cured (or crosslinked)organic matrix, or a thermoplastic organic matrix. Correspondingly, eachlayer of the optical elements of the present invention can be selectedfrom cured (or crosslinked) layers and thermoplastic layers. The organicmatrix of each layer of the optical elements of the present inventioncan include linkages such as, but not limited to, ether linkages;carboxylic acid ester linkages; urethane linkages; amide linkages; urealinkages; carbonate linkages; linkages formed from the radicalpolymerization of radically polymerizable ethylenically unsaturatedgroups, such as, but not limited to, vinyl groups, allyl groups, and/or(meth)acrylate groups; and combinations of two or more thereof.

Each layer of the optical elements of the present invention can beformed by art-recognized methods, such as, but not limited to,lamination methods and coating methods. Coating methods include, but arenot limited to, spray coating methods; spin coating methods; curtaincoating methods; dip coating methods; micro-jet coating methods (such asink-jet coating methods); in-mold coating methods; and combinationsthereof. Lamination methods include, but are not limited to, extrusionlamination methods (such as directly over the substrate); in-moldlamination methods (in which a laminate is placed in a mold, and thesubstrate is formed there-against within the mold); thermal laminationmethods (in which a laminate is thermally fused over the substrate);adhesive lamination methods (in which the laminate is adhered over thesubstrate by an interposed adhesive layer); and combinations thereof.

With some embodiments of the present invention, the optical elementfurther includes an alignment layer interposed between the substrate andthe layer (which includes a mesogen-containing compound of the presentinvention), in which the alignment layer is at least partially alignableby exposure to at least one of a magnetic field, an electric field,linearly polarized radiation, shear force, or combinations of two ormore thereof. Classes and examples of materials that can be used as orto form the alignment layer include, but are not limited to, theorientation facilities, orientation materials, alignment media, andalignment facilities described at: column 5, line 5 through column 6,line 4; column 7, line 56 through column 24, line 36; and the examplesof U.S. Pat. No. 8,926,091 B2, which disclosure is incorporated hereinby reference.

The optical element of the present invention can, with some embodiments,include

one or more additional layers, such as, but not limited to, primerlayer(s), antireflective layer(s), protective layer(s), and hardcoatlayer(s), polarizing layer(s). Classes and examples of such additionaloptional layers are described at column 20, line 30 through column 21,line 38 of U.S. Pat. No. 8,828,284 B2, which disclosure is incorporatedherein by reference.

With some embodiments, the optical element of the present invention isselected from an ophthalmic element, a display element, a window, amirror, and a liquid crystal cell element.

With some further embodiments, the ophthalmic element of the presentinvention is selected from a corrective lens, a non-corrective lens, acontact lens, an intra-ocular lens, a magnifying lens, a protectivelens, and a visor.

The present invention can be further characterized by one or more of thefollowing non-limiting clauses 1-16.

Clause 1: A mesogen-containing compound represented by the followingFormula (I),

wherein:

(A) Mesogen-1 is represented by the following Formula (II),

wherein:

-   -   R is selected from hydrogen, alkyl, and alkoxy; and    -   e′ and f′ for each occurrence for Formula (II), are        independently from 0 to 4, provided the sum of e′ and f′ is at        least 2;

(B) Mesogen-2 is represented by Formula (II) of Mesogen-1, or thefollowing Formula (III),

wherein:

-   -   P is selected from R, acrylate, methacrylate,        trihalomethacrylate, oxirane, hydroxyl, amino, carboxylic acid,        and carboxylic acid ester;    -   d is 0 to 20;    -   S₁ independently for each d is selected from an S₁-spacer unit        chosen from —(CH₂)—; —O—; —C(O)—; and —NH—, provided that when        two S₁-spacer units comprising heteroatoms are linked together,        the S₁-spacer units are linked so that heteroatoms are not        directly linked to each other;

Q₁ is a divalent group selected from the group consisting ofunsubstituted or substituted cycloaliphatic group; unsubstituted orsubstituted heterocycloaliphatic group; unsubstituted or substitutedaryl; and unsubstituted or substituted heteroaryl; wherein thecycloaliphatic group substituents, heterocycloaliphatic groupsubstituents, aryl substituents, and heteroaryl substituents are eachindependently selected from alkyl and halogen; and

e″ and f″ for each occurrence for Formula (III) are independently from 0to 6, provided the sum of e″ and f″ is at least 2;

wherein independently for each of Formula (II) and Formula (III),

-   -   (i) Q₂ and Q₃ for each occurrence are independently a divalent        group selected from the group consisting of unsubstituted or        substituted cycloaliphatic group; unsubstituted or substituted        heterocycloaliphatic group; unsubstituted or substituted aryl;        and unsubstituted or substituted heteroaryl; wherein the        cycloaliphatic group substituents, heterocycloaliphatic group        substituents, aryl substituents, and heteroaryl substituents are        each independently selected from alkyl and halogen;    -   (ii) S₂, S₃, and S₄ for each occurrence are independently        selected from a spacer unit chosen from —(CH₂)—; —O—; —C(O)—;        and —NH—; and    -   (iii) e, f, and g for each occurrence are independently 0 to 3,        provided that when two spacer units comprising heteroatoms are        linked together the spacer units are linked so that heteroatoms        are not directly linked to each other;

(C) -L- is represented by the following Formula (IV),

-(A-B)_(y)-E-  (IV)

wherein:

-   -   (i) y is 1 to 30;    -   (ii) each A independently for each y is a divalent group        selected from the group consisting of aliphatic group and        haloaliphatic group;    -   (iii) each B independently for each y is a divalent group        selected from the group consisting of —O—; —C(O)O—; —OC(O)O—;        —C(O)N(R₁)- where R₁ is H or alkyl; —NH—C(O)O—; —N(R₂)C(O)N(R₂)-        where each R₂ is independently selected from H or alkyl;

where n is 1 to 5, and each R₃ independently for each n is selected frommethyl, ethyl, and phenyl; —Si(R₄)(R₄)- where each R₄ is independentlyselected from methyl, ethyl, and phenyl; unsubstituted or substitutedcycloaliphatic groups; unsubstituted or substituted aryl; andunsubstituted or substituted —O—(Aryl)—O—; wherein the cycloaliphaticsubstituents, the aryl substituents, and —O—(Aryl)—O—substituents areeach independently selected from alkyl, and —(S₁)_(d)-P, where S₁, d andP are each as defined with regard to Formula (III); and

-   -   (iv) E is a divalent group selected from the group consisting of        aliphatic group and haloaliphatic group.

Clause 2: The mesogen-containing compound of clause 1, wherein:

(B) for Formula (III),

-   -   Q₁ is a divalent group selected from the group consisting of        unsubstituted or substituted cycloalkyl; unsubstituted or        substituted phenyl; unsubstituted or substituted naphthyl; and        unsubstituted or substituted triptycenyl; wherein the cycloalkyl        substituents, phenyl substituents, naphthyl substituents, and        triptycenyl substituents are each independently selected from        alkyl and halogen; and        wherein independently for each of Formula (II) and Formula        (III),

Q₂ and Q₃ for each occurrence are independently a divalent groupselected from the group consisting of unsubstituted or substitutedcycloalkyl; unsubstituted or substituted phenyl;

unsubstituted or substituted naphthyl; and unsubstituted or substitutedtriptycenyl; wherein the cycloalkyl substituents, phenyl substituents,naphthyl substituents, and triptycenyl substituents are eachindependently selected from alkyl and halogen.

Clause 3: The mesogen-containing compound of clause 2, wherein:

for Formula (III), Q₁ is a divalent group selected from the groupconsisting of unsubstituted or substituted 1,4-cyclohexyl; unsubstitutedor substituted 1,4-phenyl; unsubstituted or substituted 1,5-naphthyl;unsubstituted or substituted 2,6-naphthyl; unsubstituted or substituted1,8-naphthyl; and unsubstituted or substituted 1,4-triptycenyl, whereinthe 1,4-cyclohexyl substituents, 1,4-phenyl substituents, 1,5-naphthylsubstituents, 2,6-naphthyl substituents, 1,8-naphthyl substituents, and1,4-triptycenyl substituents are each independently selected from alkyland halogen; and

independently for each of Formula (II) and Formula (III),

Q₂ and Q₃ for each occurrence are independently a divalent groupselected from the group consisting of unsubstituted or substituted1,4-cyclohexyl; unsubstituted or substituted 1,4-phenyl; unsubstitutedor substituted 1,5-naphthyl; unsubstituted or substituted 2,6-naphthyl;

unsubstituted or substituted 1,8-naphthyl; and unsubstituted orsubstituted 1,4-triptycenyl, wherein the 1,4-cycloalkyl substituents,1,4-phenyl substituents, 1,5-naphthyl sub stituents, 2,6-naphthylsubstituents, 1,8-naphthyl substituents, and 1,4-triptycenylsubstituents are each independently selected from alkyl and halogen.

Clause 4: The mesogen-containing compound of clause 3, wherein:

(A) for Formula (II),

-   -   R is selected from hydrogen and alkyl;

(B) for Formula (III),

-   -   P is selected from R, acrylate, and methacrylate;

(C) for Formula (IV),

-   -   (ii) each A independently for each y is a divalent group        selected from the group consisting of alkyl and haloalkyl;    -   (iii) each B independently for each y is a divalent group        selected from the group consisting of —O—; —C(O)O—; —OC(O)O—;        —C(O)N(R₁)- where R₁ is H or alkyl; —NH—C(O)O—;        —N(R₂)C(O)N(R₂)- where each R₂ is independently selected from H        or alkyl;

where n is 1 to 5, and each R₃ independently for each n is selected frommethyl and phenyl; —Si(R₄)(R₄)- where each R₄ is independently selectedfrom methyl and phenyl; unsubstituted or substituted cycloalkyl (suchas, but not limited to, unsubstituted or substituted cyclohexyl);unsubstituted or substituted phenyl; and unsubstituted or substituted—O—(Phenyl)—O—; wherein the cycloalkyl substituents, the phenylsubstituents, and —O—(Phenyl)—O- substituents are each independentlyselected from alkyl, and —(S₁)_(d)P, where S₁, d and P are each asdefined with regard to Formula (III); and

-   -   (iv) E is a divalent group selected from the group consisting of        alkyl groups and haloalkyl groups.

Clause 5: The mesogen-containing compound of clauses 1, 2, 3, or 4,wherein provided that for Formula (IV), no B or only one B is a divalentgroup selected from the group consisting of unsubstituted or substitutedcycloaliphatic groups; unsubstituted or substituted aryl; andunsubstituted or substituted —O—(Aryl)—O—.

Clause 6: The mesogen-containing compound of clauses 1, 2, 3, 4, or 5,wherein provided that for Formula (IV), no B or only one B is a divalentgroup selected from the group consisting of unsubstituted or substitutedcycloalkyl groups (such as, but not limited to, unsubstituted orsubstituted cyclohexyl groups); unsubstituted or substituted phenyl;unsubstituted or substituted naphthyl; and unsubstituted or substituted—O—(Phenyl)—O—.

Clause 7: The mesogen-containing compound of clauses 1, 2, 3, 4, 5, or6, wherein Mesogen-2 is represented by Formula (II) of Mesogen-1.

Clause 8: The mesogen-containing compound of any one of clauses 1-7,wherein Mesogen-2 is represented by Formula (II) of Mesogen-1, andMesogen-1 and Mesogen-2 are the same.

Clause 9: The mesogen-containing compound of any one of clauses 1-8,wherein -L- comprises at least 20 bonds.

Clause 10: A liquid crystal composition comprising themesogen-containing compound of any one of clauses 1-9.

Clause 11: The liquid crystal composition of clause 10, furthercomprising at least

one of a photochromic compound, a dichroic compound, and aphotochromic-dichroic compound.

Clause 12: The liquid crystal composition of clause 11, wherein thephotochromic-dichroic compound comprises at least one photochromicmoiety, and said photochromic compound and each photochromic moiety ofsaid photochromic-dichroic compound are in each case independentlyselected from indeno-fused naphthopyrans, naphtho[1,2-b]pyrans,naphtho[2,1-b]pyrans, spirofluoroeno[1,2-b]pyrans, phenanthropyrans,quinolinopyrans, fluoroanthenopyrans, spiropyrans, benzoxazines,naphthoxazines, spiro(indoline)naphthoxazines,spiro(indoline)pyridobenzoxazines, spiro(indoline)fluoranthenoxazines,spiro(indoline)quinoxazines, fulgides, fulgimides, diarylethenes,diarylalkylethenes, diarylalkenylethenes, non-thermally reversiblephotochromic compounds, and mixtures thereof.

Clause 13: An optical element comprising:

a substrate; and

a layer on at least a portion of a surface of said substrate, whereinsaid layer comprises the mesogen-containing compound of any one ofclauses 1-9.

Clause 14: The optical element of clause 13, further comprising analignment layer

interposed between the substrate and said layer, wherein the alignmentlayer is at least partially alignable by exposure to at least one of amagnetic field, an electric field, linearly polarized radiation, shearforce, or combinations of two or more thereof.

Clause 15: The optical element of clauses 13 or 14, wherein the opticalelement is selected from an ophthalmic element, a display element, awindow, a mirror, and a liquid crystal cell element.

Clause 16: The ophthalmic element of claim 15, wherein the ophthalmicelement is selected from a corrective lens, a non-corrective lens, acontact lens, an intra-ocular lens, a magnifying lens, a protectivelens, and a visor.

The present invention is more particularly described in the followingexamples, which are intended as illustrative only, since numerousmodifications and variations therein will be apparent to those skilledin the art.

EXAMPLES

In Part 1a of the following examples, the preparation ofmesogen-containing portions or segments is described. In Part lb thereis described the preparation of two non-mesogenic diols that were usedin the preparation of mesogen-containing compounds according to someembodiments of the present invention. In Part 2 there is described thepreparation of mesogen-containing compounds, which include anon-mesogenic linking group (-L-) that connects (covalently bonds)together two separate mesogen-containing portions or segments. In Part 3there is described the preparation of liquid crystal coatingformulations. In Part 4 there is described the preparation of coatedsubstrates (test specimens). In Part 5 there is described thephotochromic performance testing of the test specimens.

Part 1a Synthesis of Mesogen-Containing Segments.

Mesogen-containing segments S1 through S9 each include a single terminal

R-substituted bicyclohexyl group or substructure,where R- is —C₅H₁₁ or —C₃H₇. Representative structures formesogen-containing segments S1 through S9 are depicted in Table 1.Mesogen-containing segments S10 through S16 do not include a terminalR-substituted bicyclohexyl group or substructure. Representativestructures for Segments S10 through S16 are depicted in Table 2.

Segment S1

4-((4-((8-Hydroxyoctyl)oxy)benzoyl)oxy)phenyl trans,trans-4′pentyl-[1,1′-bi(cyclohexane)]-4-carboxylate was prepared inaccordance with Example 1, steps 1 through 8 of United States PatentApplication Publication No. 2017/0275534 A1, which particular disclosureof which is incorporated herein by reference.

Segment S2

To a one-neck, round bottom flask containing Segment S1 (400 g) andsuccinic anhydride (74.0 g) was added toluene (1.5 L) and triethylamine(“Et₃N,” 15.0 mL). The suspension was heated to 80° C. and stirred for 5hours. The reaction mixture was poured into hot ethyl acetate (“EtOAc,”1.5 L, 65° C.) over 5 minutes while stirring, then the flask was rinsedwith tetrahydrofuran (“THF,” 100 mL). The resulting solution was allowedto cool to room temperature and crystallized overnight to yield 410 g ofproduct (yield 88%). By ¹H NMR analysis it was determined that theproduct had a structure consistent with4-oxo-4-((8-(4-((4-((4′-pentyl-[1,1′-bi(cyclohexane)]-4-carbonyl)oxy)phenoxy)carbonyl)phenoxy)octyl)oxy)butanoic acid.

Segment S3 Step 1

The procedures of Example 1, steps 1 through 8 of United States PatentApplication Publication No. 2017/0275534 A1 were followed, substitutingequimolar amounts of ⅔-methyl-4-((tetrahydro-2H-pyran-2-yl)oxy)phenol inplace of 4-((tetrahydro-2H-pyran-2-yl)oxy)phenol in step 2, and4′-((6-((tetrahydro-2H-pyran-2-yl)oxy)hexyl)oxy)-[1,1′-biphenyl]-4-carboxylicacid in place of 4-(8-(tetrahydro-2H-pyran-2-yloxy)octyloxy)-benzoicacid in step 7. This yielded⅔-methyl-4-((4′-pentyl-[1,1′-bi(cyclohexane)]-4- carbonyl)oxy)phenyl4′-((6-hydroxyhexyl)oxy)-[1,1′-biphenyl]-4-carboxylate.

Step 2

The product of step 1 above was subjected to the same reactionconditions described for Segment S2 above to yield4-((6-((4′-((⅔-methyl-4-((4′-pentyl-[1,1′-bi(cyclohexane)]-4-carbonyl)oxy)phenoxy)carbonyl)-[1,1′-biphenyl]-4-yl)oxy)hexyl)oxy)-4-oxobutanoicacid.

Segment S4 Step 1

Pyridine (24.1 g), 4-(4′-pentyl-[1,1′-bi(cyclohexan)]-4-yl)phenol (50.0g), and dichloromethane (“DCM,” 250 mL) were mixed and cooled to 0° C.,after which trifluoromethanesulfonic anhydride (51.5 g) in DCM (250 mL)was added dropwise. The mixture was warmed to room temperature andallowed to stir for 10 hours. The resulting mixture was washed withbrine and dried over MgSO₄. The solvent was removed and the residue waspassed through a short pad of silica. The crude product was precipitatedfrom EtOAc and methanol (“MeOH”) at −10° C. Yield: 65 g.

Step 2

To a one-neck, round bottom flask containing the product of Step 1 (30.0g), 4-carboxyphenylboronic acid (13.0 g) and Na₂CO₃ (42.0 g), was addeda solution of 1,2-dimethoxyethane (200 mL) and water (200 mL). Thesuspension was purged with nitrogen for 10 minutes before Pd(PPh₃)₄(3.75 g) was added, then stirred at 75° C. for 18 hours. This was addedto water and the precipitate was recrystallized from a mixture of THF,EtOAc, and ethanol (“EtOH”) followed by recrystallization from acetone.Yield: 25 g.

Segment S5 Step 1

Synthesis of4′-(4′-pentyl[1,1′-bi(cyclohexan)]-4-yl)-[1,1′-biphenyl]-4-ol wasaccomplished following a procedure similar to Step 2 of Segment 4 above,using the following reagents: product from Step 1 of Segment 4 (30.0 g),(4-hydroxyphenyl)boronic acid (10.0 g), Pd(PPh₃)₄ (1.50 g), Na₂CO₃ (18.0g), and Bu₄NI (1.20 g).

Step 2

To a one-neck, round bottom flask containing the product from Step 1(30.0 g, 74.1 mmol) was added 6-bromohexanol (26.9 g), Bu₄NI (1.0 g),K₂CO₃ (20.5 g), and THF (250 mL). After stirring under reflux overnight,the suspension was added to cold water. The precipitate was filtered.The residue was dissolved in DCM and the aqueous phase removed. Thesolvent was removed and recrystallized from toluene (300 mL) and EtOAc(200 mL) and washed with cold EtOAc, providing a yield of 17 g of6((4′-(4′-pentyl-[1,1′-bi(cyclohexan)]-4-yl)-[1,1′-biphenyl]-4-yl)oxy)hexan-1-ol.

Step 3

The product of step 2 above was subjected to the same reactionconditions described for Segment S2 above to yield Segment S5 (20.0 g).

Segment S6 Step 1

The product of Step 3 from Example 1 of United States Patent ApplicationPublication No. 2017/0275534 A1 (20.0 g), 4-formylbenzoic acid (8.46 g),4-dimethylaminopyridine (“DMAP,” 0.65 g), and DCM (250 mL) was addedN,N′-dicyclohexylcarbodiimide (“DCC,” 12.1 g). After stirring overnight,the formed dicyclohexylurea was removed and the filtrate passed througha silica plug (eluent was DCM). The resulting solid was dissolved inEtOAc and filtered.

Step 2

To the product of Step 1 (25.0 g) was added KMnO₄ (15.6 g, in water),followed by heating at 60° C. in air for 3 hours. After cooling, thereaction mixture was added to water and acidified with 1N HCl. Theprecipitated product was filtered and washed with water thenrecrystallized from THF, EtOAc and EtOH. Yield: 22g.

Segment S7 Step 1

A solution of 4-(3,5-difluorophenyl)-4′-propyl-1,1′-bi(cyclohexane)(15.00 g) in THF (125 mL) was cooled to −75° C. under nitrogen. To thiswas added n-BuLi (2.50 M, 21.0 mL) slowly. The solution was kept at −78°C. for about 30 minutes before Br₂ (3.0 mL) was added slowly. Theresulting solution was allowed to warm to room temperature overnight,then washed with aqueous sodium bisulfite. The aqueous layer wasextracted with EtOAc (3×50 mL). The combined organic extracts werewashed with brine, dried over MgSO₄, and filtered through celite to givean off-white solid. Yield: 19.42 g.

Step 2

Synthesis of2-((2′,6′-difluoro-4′-(4′-propyl-[1,1′-bi(cyclohexan)]-4-yl)-[1,1′-biphenyl]-4-yl)oxy)tetrahydro-2H-pyranwas accomplished following a procedure similar to Step 2 of Segment S4above using the following reagents: product of Step 1 (17.23 g);(4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)boronic acid (10.05 g); K₂CO₃(17.90 g); toluene (300 mL); EtOH (100 mL); water (10 mL); and Pd(PPh₃)₄(0.99 g).

Step 3

The product from Step 2 was dissolved in a solution of THF/MeOH/EtOH(150 mL/20 mL/20 mL) before HCl (1N, 4.0 mL) was added dropwise. Afterstirring at room temperature for about 45 minutes, water was added (200mL). The formed precipitate was collected via filtration and dried undervacuum. Yield: 17.66 g.

Step 4

Synthesis of6-((2′,6′-difluoro-4′-(4′-propyl-[1,1′-bi(cyclohexan)]-4-yl)-[1,1′-biphenyl]-4-yl)oxy)hexan-1-olwas accomplished following a procedure similar to Step 2 of Segment S5above, using the following reagents: product from Step 3 (17.66 g),6-chlorohexan-1-ol (22.84 g), K₂CO₃ (21.29 g), KI (1.77 g) and THF (150mL). Yield: 16.71 g.

Step 5

The product of Step 4 was subjected to similar reaction conditions asSegment S2 to yield4-((1-((2′,6′-difluoro-4′-(4′-propyl-[1,1+-bi(cyclohexan)]-4-yl)-[1,1′-biphenyl]-4-yl)oxy)butan-2-yl)oxy)-4-oxobutanoicacid.

Segment S8 Step 1

Synthesis of 4-(4-hydroxycyclohexyl)-⅔-methylphenyl4′-pentyl-[1,1′-bi(cyclohexane)]-4-c arboxylate was accomplishedfollowing a procedure similar to Step 1 of Segment S6 above, using thefollowing reagents: 4-(4-hydroxycyclohexyl)-⅔-methylphenol (44.1 g),4′-pentyl-[1,1′-bi(cyclohexane)]-4-carboxylic acid (50.0 g), DCC (40.4g), DMAP (2.6 g), DCM (500 mL). Yield: 40.0 g.

Step 2

Synthesis of⅔-methyl-4-(4-((4-((8-((tetrahydro-2H-pyran-2-yl)oxy)octyl)oxy)benzoyl)oxy)cyclohexyl)phenyl4′-pentyl[1,1′-bi(cyclohexane)]-4-carboxylate was accomplished followinga procedure similar to Step 1 of Segment S6 above, using the followingreagents: product from Step 1 (30.0 g),4-((8-((tetrahydro-2H-pyran-2-yl)oxy)octyl)oxy)benzoic acid (25.0 g),DCC (15.8 g), DMAP (1.6 g), DCM (300 mL). Yield: 37.0 g.

Step 3

The product of Step 2 (35.0 g) was suspended in EtOH/THF (100 mL/200 mL)before 4-toluenesulfonic acid (“TsOH,” 2.5 g) was added. After refluxingfor 3 hours the solution was concentrated and then added to water. Theresulting precipitate was filtered, dried, and recrystallized fromTHF/EtOAc to yield segment 8. Yield: 22.0 g.

Segment S9 Step 1

The procedures of Example 1 from U.S. Patent No. 2017/0275534, werefollowed, substituting an equimolar amount of4-((6-((tetrahydro-2H-pyran-2-yl)oxy)hexyl)oxy)cyclohexane-1-carboxylicacid in place of 4-(8-(tetrahydro-2H-pyran-2-yloxy)octyloxy)-benzoicacid in step 7 to yield4-((4-((6-hydroxyhexyl)oxy)cyclohexane-1-carbonyl)oxy)phenyl4′-pentyl-[1,1′-bi(cyclohexane)]-4-carboxylate.

Step 2

The product of Step 1 was subjected to the reagents and reactionconditions used in Segment S2 to yield4-oxo-4-((6-((4-((4-((4′-pentyl-[1,1′-bi(cyclohexane)]-4-carbonyl)oxy)phenoxy)carbonyl)cyclohexyl)oxy)hexyl)oxy)butanoicacid.

TABLE 1 Representative Structures of Mesogen-Containing Segments S1through S9 Segment No. Representative Structure S1

S2

S3

S4

S5

S6

S7

S8

S9

Segment S10

4-((4-((6-(Acryloyloxy)hexyl)oxy)benzoyl)oxy)phenyl4-((8-hydroxyoctyl)oxy)benzoate was prepared using the procedures ofSteps 1 through 6 of Example 2 in U.S. Pat. No. 8,349,210 B2, exceptthat 6-chlorohexan-1-ol and 8-chlorohexan-1-ol were used in place of3-chloropropan-1-ol in Step 1 and 6-chlorohexan-1-ol in Step 3,respectively.

Segment S11 Step 1

4-((4-((6-(Acryloyloxy)hexyl)oxy)benzoyl)oxy)-⅔-methylphenyl4-((tetrahydro-2H-pyran-2-yl)oxy)benzoate was made in accordance withStep 1 of Segment S6 using the following quantities:4-hydroxy-⅔-methylphenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate (12.0 g,30.0 mmol), 4-((tetrahydro-2H-pyran-2-yl)oxy)benzoic acid (6.7 g),2-(dimethylamino)pyridinium p-toluenesulfonate (“DPTS,” 1.0 g), DCM (300mL), and DCC (8.2 g,).

Step 2

4-((4-((6-(Acryloyloxy)hexyl)oxy)benzoyl)oxy)-⅔-methylphenyl4-hydroxybenzoate was made in accordance with Step 3 of Segment S8 usingthe following materials: product from Step 1, TsOH (0.57 g), DCM (150mL), MeOH (150 mL).

Step 3

4-((4-((6-(Acryloyloxy)hexyl)oxy)benzoyl)oxy)-⅔-methylphenyl4-((4-((6-((tetrahydro-2H-pyran-2-yl)oxy)hexyl)oxy)cyclohexane-1-carbonyl)oxy)benzoatewas made in accordance with Step 1 of Segment S11 using the followingquantities: product from Step 2 (37.0 g),4-((6-((tetrahydro-2H-pyran-2-yl)oxy)hexyl)oxy)cyclohexane-1-carboxylicacid (28.1 g), DCC (19.1 g), DMAP (1.2 g), DCM (500 mL).

Step 4

4-((4-((6-(Acryloyloxy)hexyl)oxy)benzoyl)oxy)-⅔-methylphenyl4-((4-((6-hydroxyhexyl)oxy)cyclohexane-1-carbonyl)oxy)benzoate was madein accordance with Step 3 of Segment S8 using the following materials:product from Step 3, TsOH (2.7 g), DCM (200 mL), MeOH (200 mL). Yield:44 g.

Segment S12 Step 1

4-((4-((4-((6-(Acryloyloxy)hexyl)oxy)benzoyl)oxy)-⅔-methylphenoxy)carbonyl)phenyl4-((6-((tetrahydro-2H-pyran-2-yl)oxy)hexyl)oxy)benzoate was made inaccordance with Step 1 of Segment S11 using the following quantities:4-hydroxy-⅔-methylphenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate (39.8 g),4-((4-((6-((tetrahydro-2H-pyran-2-yl)oxy)hexyl)oxy)benzoyl)oxy)benzoicacid (44.3 g), DCC (24.7 g), DMAP (2.4 g), DCM (1 L).

Step 2

4-((4-((4-((6-(Acryloyloxy)hexyl)oxy)benzoyl)oxy)-⅔-methylphenoxy)carbonyl)phenyl4-((6-hydroxyhexyl)oxy)benzoate was made in accordance with Step 2 ofSegment S8 using the following quantities: product from step 1, TsOH(3.8 g), DCM (200 mL), MeOH (200 mL).

Segment S13

4-((4-((8-Hydroxyoctyl)oxy)benzoyl)oxy)phenyl4-((6-(methacryloyloxy)hexyl)oxy)benzoate was made using the proceduresof Steps 1 through 6 of Example 2 in U.S. Pat. No. 8,349,210 B2, exceptthat 6-chlorohexan-1-ol was used in place of 3-chloropropan-1-ol in Step1, methacrylic acid was used in place of acrylic acid in Step 2, and8-chlorohexan-1-ol was used in place of 6-chlorohexan-1-ol in Step 3.

Segment S14

4′ -(Trans-4-pentylcyclohexyl)-[1,1′-biphenyl]-4]carboxylic acid wasprepared in accordance with Example 1, Step 5 in United States PatentApplication Publication No. US 2012/0002141 A1.

Segment S15

Trans-4-(((4′-(trans-4-pentylcyclohexyl)-[1,1′-biphenyl]-4-yl)oxy)carbonyl)cyclohexanecarboxylicacid was prepared in accordance with Example 8, Step 2 in United StatesPatent Application Publication No. US 2012/0002141 A1.

Segment S16

To a one-neck, round bottom flask containing4-((4-((6-((tetrahydro-2H-pyran-2-yl)oxy)hexyl)oxy)benzoyl)oxy)benzoicacid (8.84 g, 20.0 mmol), 4-hydroxyphenyl4-((6-hydroxyhexyl)oxy)benzoate (6.60 g), DPTS (0.62 g), DCM (100 mL),and THF (100 mL) was added DCC (5.36 g). After stirring overnight, theformed dicyclohexylurea was filtered away and the filtrate passedthrough a silica plug (eluent was DCM/EtOAc). The resulting solid wasrecrystallized from EtOAc (12.3 g, 81%).

TABLE 2 Representative Structures of Mesogen-Containing Segments S10through S16 Segment No. Representative Structure S10

S11

S12

S13

S14

S15

S16

Part 1b Synthesis of Non-Mesogenic Diols

The preparation of non-mesogenic diols D-1 and D-2 is described asfollows. Representative structures for diols D-1 and D-2 are provided inTable A.

Diol D-1 Step 1

To a reaction flask containing 6-bromohexyl methacrylate (25.00 g),2,5-dihyroxybenzoic acid (15.46 g), trimethylamine (Et₃N) (10.66 g), anda catalytic amount of 4-methyl-2,6-di-tert-butyl phenol (0.5 g) wasadded N,N-dimethylformamide (“DMF,” 100 mL). After heating at 90° C. for4 hours, the resulting solution was poured into water (200 mL, 0° C.).After extracting with EtOAc (150 mL×3), the combined organic layer waswashed with brine (200 mL×3) and dried over MgSO₄. Filtration through ashort pad of silica followed by removal of the solvent offered theproduct in a form of light brown liquid. Yield: 33 g.

Step 2

Synthesis of 6-(methacryloyloxy)hexyl2,5-bis((6-hydroxyhexyl)oxy)benzoate was accomplished following aprocedure similar to Step 2 of Segment S5 above, using the followingreagents: product from Step 1 (10.0 g), 6-bromohexan-1-ol (12.3 g), andBu4NI (2.3 g), butanone (100 mL), and K₂CO₃ (12.8 g). Yield: 8 g.

Diol D-2 Step 1

Triptycene-1,4-hydroquinone was prepared in accordance with compound 2from J. Mat. Chem. A, 2014, 2, 13309-13320.

Step 2

Synthesis of8,8′4(9,10-dihydro-9,10-[1,2]benzenoanthracene-1,4-diyl)bis(oxy))bis(octan-1-ol)was accomplished following a procedure similar to Step 2 of Segment S5above, using the following reagents: product from Step 1 (30.0 g),8-chlorooctan-1-ol (51.7 g), KI (3.48 g), DMF (200 mL), and K₂CO₃ (72.4g). Yield: 60 g.

TABLE A Diol No. Representative Structure D-1

D-2

Part 2. Synthesis of Mesogen-Containing Compounds Part 2a:

The reaction of acid-functional mesogen-containing groups/segments withdiols to

form symmetrical mesogen-containing compounds (Examples 1-16), isdescribed as follows.

The following general procedure was followed. A diol (one molarequivalent), an acid-functional mesogen-containing groups/segments (oracid-functional mesogen intermediates) (2.0 equivalents), TsOH (0.5equivalents), and DMAP (0.5 equivalents) were combined in DCM sufficientto provide approximately 35% dilution by weight. Once a homogeneoussolution was achieved, DCC (2.3 equivalents) was added in one portion.After stirring overnight under nitrogen, dicyclohexylurea precipitatewas removed and the filtrate partially concentrated before being passedthrough a plug of silica. The material was dissolved in EtOAc andfiltered through celite, then precipitated from MeOH/EtOAc to give thedesired product. Various combinations of acid functional mesogenintermediates (acid-functional mesogen-containing groups/segments) anddiols described as summarized in Table 3, were synthesized by thisprocedure. ¹H NMR was used to confirm all product structures as well asthe oligomer lengths in purified products.

TABLE 3 Acid Functional Mesogen- Containing Segment (2 eq) Diol (1 eq)Yield Example 1  S2 Poly(THF) 1000¹ 91% Example 2  S2 Poly(THF) 1400²62% Example 3  S2 Poly(THF) 2000³ 69% Example 4  S9 Poly(THF) 1000 76%Example 5  S3 Poly(THF) 1000 75% Example 6  S6 Poly(THF) 1000 66%Example 7  S7 Poly(THF) 1000 62% Example 8  S2 ETERNACOLL ® UH100⁴ 38%Example 9  S2 ETERNACOLL PH100D⁵ 49% Example 10 S2 ETERNACOLL UH200⁶ 95%Example 11 S2 Urethane Diol⁷ 73% Example 12 S2 Diol D-1 49% Example 13S2 cyclohexanediester diol⁸ 77% Example 14 S2 perfluoroadipicacid diol⁹78% Example 15 S2 tetramethylsiloxane diol¹⁰ 67% Example 16 S2cyclohexylurethane diol¹¹ 68% ¹A poly tetrahydrofuran with approximateMn of 1000. ²A poly tetrahydrofuran with approximate Mn of 1400. ³A polytetrahydrofuran with approximate Mn of 2000. ⁴A polycarbonate diol withhexyl repeat units, with an approximate Mn of 1000, available from UBEIndustries, Ltd. ⁵A polycarbonate diol with hexyl and pentyl repeatunits, with an approximate Mn of 1000, available from UBE Industries,Ltd. ⁶A polycarbonate diol with hexyl repeat units, with an approximateMn of 2000, available from UBE Industries, Ltd. ⁷A urethane diol wasprepared by reacting three equivalents of 1,6-hexanediol with twoequivalents of 2,2,4-trimethylhexamethylene diisocyanate in the presenceof a tin catalyst. ⁸A cyclohexanediester diol was prepared by reactingfour equivalents of 1,10-decanediol with three equivalents oftrans-cyclohexane-1,4-dicarboxylic acid in the presence of a tincatalyst. ⁹A perfluoroadipicacid diol was prepared by reacting fourequivalents of 1,10-decanediol with three equivalents of perfluoroadipicacid in the presence of a tin catalyst. ¹⁰A tetramethylsiloxane diol wasprepared by reacting three equivalents of 3,3′-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-ol) with two equivalents ofadipoyl chloride in the presence of Et₃N and DMAP. ¹¹Acyclohexylurethane diol was prepared by reacting three equivalents of1,10-decanediol with four equivalents of isophorone diisocyanate in thepresence of a tin catalyst.

Part 2b.

Additional mesogen-containing compounds (Examples 17-21) were preparedin accordance with the following general procedure. A diol compound (1equivalent) was dissolved in DCM along with ϵ-caprolactone in the molarratios as summarized in Table 4. To this was added diphenyl phosphate(DPP) (0.5 equivalents) and the mixture was stirred under nitrogen for4-8 hours (or until the required number of caprolactone units has beenreached) to form a polyester diol, which was then reacted with the acidfunctional mesogen Segment S2 (2.05 equivalents) under the conditionsdescribed in Part 2a above. The components, equivalent ratios, andyields are summarized in Table 4. ¹H NMR analysis was used to confirmall product structures as well as the oligomer lengths in the purifiedproducts.

TABLE 4 Diol ε-caprolactone Segment S2 (1 equivalent) equivalents(equivalents) Yield Example 17 1,6-hexanediol 8.0 2.05 51% Example 18Tetraethyleneglycol 6.0 2.1  25% Example 19 Poly(THF) 1000 5.0 2.5  57%Example 20 Diol D-1 6.0 2.2  46% Example 21 Diol D-2 6.0 2.3  48%

Part 2c.

Mesogen-containing compounds (Examples 22-24) with polyester segments(or linking groups) were prepared by combining two equivalents of thehydroxyl functional mesogen Segment S1 with ϵ-caprolactone in DCMfollowed by addition of DPP (1 equivalent). The mixture was stirred forfour hours, followed by addition of a diacid compound (1 equivalent),DMAP (1 equivalent) and DCC (3 equivalent). After stirring overnight,dicyclohexylurea precipitate was removed and the product purified byprecipitation from a mixture of EtOAc and MeOH (1:8 v/v). Reagents andmolar ratios used for this reaction series are summarized in Table 5. ¹HNMR was used to confirm all product structures as well as the oligomerlengths in the purified products.

TABLE 5 Segment S1 ε-caprolactone Equivalents equivalents Diacid (1 eq)Yield Example 22 2 8 4,4′-(1,1,3,3- 48% tetramethyldisiloxane-1,3-diyl)dibutyric acid Example 23 2 8 7,7,9,9,10,10,12, 62%12,13,13,15,15- dodecafluoro- 4,18-dioxo- 5,8,11,14,17- pentaoxa-henicosanedioic acid Example 24 2 8 4,4′-((2,2,3,3,4,4,5,5- 94%octafluorohexane- 1,6-diyl) bis(oxy))bis(4- oxobutanoic acid)

Mesogen-containing compounds (Examples 25-40) with polyester orpolycarbonate segments (or linking groups) were also prepared in astepwise manner. A hydroxy functional mesogen segment (1 equivalent) wascombined with a lactone or cyclic carbonate in DCM followed by additionof DPP (0.5 equivalent). The mixture was stirred for three hours,followed by addition of an acid functional mesogen segment (1equivalent), DMAP (0.5 equivalent) and DCC (1 equivalent). Afterstirring overnight, dicyclohexylurea precipitate was removed and theproduct purified by filtering through celite and precipitation fromMeOH. Reagents and molar ratios used for this reaction series aresummarized in Table 6. ¹H NMR was used to confirm all product structuresas well as the oligomer lengths in the purified products.

TABLE 6 Hydroxy Acid functional Equivalents functional Mesogen ofMesogen Segment Lactone or lactone or Segment (1 eq) carbonate carbonate(1 eq) Yield Example 25 S10 ε-caprolactone  4 S2  46% Example 26 S10ε-caprolactone  8 S2  95% Example 27 S10 ε-caprolactone 12 S2  92%Example 28 S13 ε-caprolactone  8 S2  83% Example 29 S11 ε-caprolactone 9 S2  66% Example 30 S12 ε-caprolactone  8 S2  89% Example 31 S10ε-caprolactone  8 S3  83% Example 32 S10 ε-caprolactone  8 S4  22%Example 33 S10 ε-caprolactone  8 S5  61% Example 34 S10 ε-caprolactone 4 S2  49% δ-valerolactone  4 Example 35 S10 trimethylene 10 S2  29%carbonate Example 36 S1  trimethylene  9 S2  86% carbonate Example 37S1  ε-caprolactone  9 S14 77% Example 38 S1  ε-caprolactone  9 S15 69%Example 39 S1  ε-caprolactone  8 S2  40% Example 40 S8  ε-caprolactone 8 S2  52%

Example 41

A further mesogenic compound according to the present invention wasprepared as follows.

Step 1

To a one-neck, round bottom flask containing Segment S1 (50.0 g), DCM(250 mL), ϵ-caprolactone (36.75 g), was added DPP (6.0 g) and stirredunder nitrogen for 4 hours. The solution was washed with NaHCO₃(saturated, 2×250 mL) and brine (1×250 ml), then dried over anhydrousMgSO₄. The solution was filtered and concentrated. The crude product wasprecipitated using EtOAc and hexanes at −10° C. Yield: 76 g.

Step 2

The product of step 1 above was subjected to the same reactionconditions described for Segment S2 above.

Step 3

The product of Step 2 (8.0 g) was subjected to similar reactionconditions as Step 1 of Segment S6 using the following reagents:1,8-dihydroxynaphthalene (0.50 g), DCC (1.6 g), DMAP (0.19 g), TsOH (0.3g), DCM (200 mL). The crude product was precipitated using ethyl acetateand methanol and dried. Yield: 3.5 g.

Example 42

An additional mesogenic compound according to the present invention wasprepared as follows.

Step 1

The product from Step 1 was made in accordance with Examples 24-39 usingthe following reagents: Segment S1 (30.0 g), DPP (6.0 g), ϵ-caprolactone(27.5 g), DCM (100 mL), 3-(allyloxy)propionic acid (8.0 g), DCC (15.0g), DMAP (2.95 g). Yield: 50.0 g.

Step 2

To a nitrogen purged schlenk tube was added the product from Step 1(15.0 g), polyphenylmethylsiloxane (PMS-H11, 5.7 g) and toluene (25 mL).Karsted's catalyst (5 drops, 2% Pt in xylenes) was added, the schlenktube was covered with aluminum foil, and the outlet sealed with a rubbercork. After stirring for 5 days, the solvent was removed and theresultant crude product dissolved in DCM before being chromatographed(eluent was 60% EtOAc in DCM). The product was dissolved in EtOAc (60mL), filtered, and then concentrated to ˜36 mL. The solution wasprecipitated by pouring into MeOH (180 mL, 0° C.). The solid wasfiltered, washed with MeOH (200 mL), and dried under vacuum. Yield: 10g.

Comparative Example CE-43:

1-{3-(4-(3-(4-(6-(4-(4-(trans-4-propylcyclohexyl)phenoxycarbonyl)phenoxy)hexyloxy)-4-oxobutanoyloxy)propyloxy)benzoyloxy)propyloxy}-4-{6-(4-(4-(trans-4-propylcyclohexyl)phenoxycarbonyl)phenoxy)hexyloxy)butane-1,4-dione,was prepared in accordance with Example 1 from U.S. Pat.. No. 8,628,685B2.

Comparative Example CE-44:

1,4-bis-{(6-(6-(6-(6-(6-(6-(trans-4-(4-(6-acryloyloxyhexyloxy)benzoyloxy)phenyl)cyclohexyloxy)hexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy}butan-1,4-dione, was preparedin accordance with Example 3 from U.S. Pat.. No. 7,910,020 B2.

Representative structures of the mesogen-containing compounds ofExamples 1-42 and Comparative Examples CE-43 and CE-44 are provided inthe following Table 7.

TABLE 7 Example Representative Structure 1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

CE-43

CE-44

Part 3. Liquid Crystal Coating Formulations Part 3a. Preparation ofStandard Liquid Crystal Coating Formulation

In suitable containers equipped with a stir bar, the first threeingredients, listed in Table 8, were charged and stirred at roomtemperature until a homogeneous solution was obtained. Then the mixtureof photochromic dichroic dyes was charged and the resulting mixture wasstirred for 1 hour at 90° C. The liquid crystal monomers were thencharged and the solution stirred for an additional hour at 90° C. Thetemperature of the solution was then reduced to 60° C. and IRGACURE 819photoinitiator was added to the solution and the mixture was stirred for30 minutes to obtain the final solution.

TABLE 8 Standard Liquid Crystal Coating (LCC) Formulation Amount (partsby Component weight) Anisole  1.995 BYK ®-322¹  0.002 4-Methoxyphenol 0.003 Photochromic dichroic dyes²  0.36 RM257³  1.26 LCM-2⁴  0.66LCM-3⁵  0.54 LCM-4⁶  0.54 IRGACURE ® 819⁷  0.045 ¹An aralkyl modifiedpoly-methyl-alkyl-siloxane available from BYK Chemie, USA. ²A mixture offive photochromic-dichroic indenofused naphthopyran dyes formulated togive a grey color on activation. ³A liquid crystal monomer4-(3-acryloyloxypropyloxy)-benzoic acid 2-methyl-1,4-phenylene ester,available commercially from EMD Chemicals, Inc.⁴4-((4-((8-((6-((6-((6-((6-((6-((6-((6-((6-(methacryloyloxy)hexanoyl)oxy)hexanoyl)oxy)hexanoyl)oxy)hexanoyl)oxy) hexanoyl)oxy) hexanoyl)oxy) hexanoyl)oxy)hexanoyl)oxy)octyl)oxy)benzoyl)oxy)phenyl4′-pentyl-[1,1′-bi(cyclohexane)]-4-carboxylate, prepared according toprocedures described in U.S Pat. No. 7,910,019B2.⁵1-(6-(6-(6-(6-(6-(6-(6-(6-(8-(4-(4-(4-(6-acryloyloxyhexyloxy)benzoyloxy)phenoxycarbonyl)phenoxy)octyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexanol,prepared in accordance with Example 17 in U.S. Pat. No. 7,910,019 B2.⁶3-methyl-4-((4-pentylcyclohexane-1-carbonyl)oxy)phenyl4-((6-(acryloyloxy)hexyl)oxy)benzoate. ⁷A photoinitiator available fromBASF.

Part 3b. Preparation of Liquid Crystal Coating Formulations IncludingMesogen-Containing Compounds:

Liquid crystal coating formulations including mesogen-containingcompounds

were prepared by adding certain mesogen-containing compounds to theStandard Liquid Crystal Coating Formulation described in Part 3a. Themixtures were prepared as summarized in the following Table 9, whereeach mesogen-containing compound was added to 5.4 parts Standard LiquidCrystal Coating Formulation. The components were combined and stirred at80° C. for 1 hour to achieve a homogeneous solution. The additivequantities are calculated based on 4.4 mol % of liquid crystal monomers.Anhydrous magnesium sulfate was then added into the solution followed bystirring at room temperature for 30 minutes. Magnesium sulfate was thenfiltered away by centrifuging and the filtrate was used for spincoating.

TABLE 9 Parts by weight of Mesogen- Mesogen- Containing ContainingExample Compound Compound Example 45 Example 1  0.342 Example 46 Example8  0.409 Example 47 Example 22 0.434 Example 48 Example 24 0.469 Example49 Example 40 0.399 Example 50 Example 12 0.333 Example 51 Example 260.375 Example 52 Example 30 0.403 Example 53 Example 31 0.388 Example 54Example 32 0.325 CE-55 CE-43 0.222 CE-56 CE-44 0.384 CE-57 None None

Part 4. Preparation of Coated Substrates

The following procedure was used to form coated substrates (testspecimens). Each liquid crystal coating formulation described in Part 3(Table 9) was spin coated at a rate of 400 revolutions per minute (rpm)for 6 seconds, followed by 1250 rpm for 6 seconds onto CR-39 ® lenssubstrates having an alignment layer. Each coated substrate was placedin an oven at 60-75° C. for 30 minutes to facilitate alignment, afterwhich they were cured under two ultraviolet lamps in a UV curing ovendesigned and built by Belcan Engineering under nitrogen while running ona conveyor belt at 2 ft/min (61 cm/min) speed at peak intensity of 0.388Watts/cm² of UVA and 0.165 Watts/cm² of UVV; and UV dosage of 7.386Joules/cm² of UVA and 3.337 Joules/cm² of UVV.

Part 5. Photochromic Performance Testing Including Absorption Ratio andOptical Response Measurements

Prior to response testing on an optical bench, the test specimens wereconditioned in a multistep custom built conditioning unit. First theywere exposed to 365 nm ultraviolet light for 10 minutes at a distance ofabout 10 cm from the source of electromagnetic radiation, in order topre-activate the photochromic compounds. The UVA irradiance at thesample was measured to be 7.7 Watts per square meter. Next, the testspecimens were heated to and held at 70° F. (21.1° C.) for 10 minutes.Finally, the heating element was turned off and F17T8 Yellow Halogenlights were turned on for 30 minutes in order to bleach, or inactivate,the photochromic compounds in the test specimens. The illuminance fromthe yellow halogen lights at the test specimen was measured to be 9.0Klux. The test specimens were then kept in a dark environment for atleast 1 hour prior to testing in order to cool and continue to fade backto a ground state.

An optical bench was used to measure the optical properties of the testspecimens and derive the absorption ratio and photochromic properties.Each test specimen was placed on the optical bench with an activatinglight source positioned at a 30° to 35° angle of incidence to thesurface of the test sample. The activating light source used was a XenonArc Lamp powered by a Newport/Oriel Model 69911 300-Watt power supplyfitted with a UNIBLITZ® VS-25 high-speed computer controlled shutterthat momentarily closed during data collection so that stray light wouldnot interfere with the data collection process, a SCHOTT® 3 mm KG-2 heatabsorbing filter, which removed short wavelength radiation, neutraldensity filter(s) for intensity attenuation and a condensing lens forbeam collimation. The arc lamp was equipped with a Digital ExposureController and sensor (Newport/Oriel model 68945) in order to maintainfine control of the output over time.

A broadband light source for monitoring response measurements waspositioned in

a perpendicular manner to the surface of the test specimen. Increasedsignal of shorter visible wavelengths was obtained by collecting andcombining separately filtered light from a 100-Watt tungsten halogenlamp (controlled by a LAMBDA® ZUP60-14 constant voltage power supply)with a split-end, bifurcated fiber optical cable. Light from one side ofthe tungsten halogen lamp was filtered with a SCHOTT® KG1 filter toabsorb heat and a HOYA® B-440 filter to allow passage of the shorterwavelengths. The other side of the light was either filtered with aSCHOTT® KG1 filter or unfiltered. The light was collected by focusinglight from each side of the lamp onto a separate end of the split-end,bifurcated fiber optic cable, and subsequently combined into one lightsource emerging from the single end of the cable. A 4 to 6 inch (10.2 to15.25 cm) light pipe was attached to the single end of the cable toinsure proper mixing. The broad band light source was fitted with aUNIBLITZ® VS-25 high-speed computer controlled shutter that momentarilyopened during data collection.

Polarization of the light source was achieved by passing the light fromthe single end of the cable through a Moxtek, PROFLUX® Polarizer held ina computer driven (analyzer polarizer), motorized rotation stage (ModelM-061.PD, M660, U651 or equivalent from Physik Instrumente). Themonitoring beam was set so that the one polarization plane)(0° wasperpendicular to the plane of the optical bench table and the secondpolarization plane)(90° was parallel to the plane of the optical benchtable. The test specimens were run in air, at 23° C.±0.1° C. (whichtemperature was maintained by a temperature controlled air cell).

To align the test specimens prepared in Part 4, a second polarizer wasadded to the optical path (research grade film polarizer, such as apolarizer from OptoSigma, SPF-50C-32).

The second polarizer was set to 90° (+/−0.1 degrees) of the firstanalyzer polarizer. The sample was placed in an air cell in aself-centering holder mounted on a rotation stage (Model M-061.PD, M660,U651 or equivalent from Physik Instrumente). A laser beam (Coherent -ULN635 diode laser) was directed through the crossed polarizers and sample.The signal intensity of the laser beam was measured, in relative countsby the spectrophotometer. The test specimen was rotated 120 degrees in 3degree increments in order to locate a minimum transmitted lightintensity of the laser beam. The test specimen was then positioned nearthe minimum transmitted light intensity and then the test specimen wasrotated 12 degrees in 0.1 degree steps in order to locate the minimumtransmission to +/−0.1 degrees, depending upon the sample quality. Thetest specimen was then finally positioned at the minimum transmissionangle. At this point the test specimen was aligned either parallel orperpendicular to the Moxtek analyzer polarizer. The second polarizer andthe diode laser beam were removed from the optical path. Using thisprocess, test specimens were aligned to ±0.1degrees prior to anyactivation.

To conduct the measurements, each test specimen was exposed to roughly6.7 W/m² of UVA from the activating light source for 15 minutes toactivate the photochromic compounds. An International Light ResearchRadiometer (Model ILT950(FC) with a detector system was used to verifyexposure at the beginning of each day. Light from the monitoring sourcethat was polarized to the 0° polarization plane was then passed throughthe sample and focused into a 1 inch (2.54 cm) integrating sphere, whichwas connected to an OCEAN OPTICS® S2000 spectrophotometer using a singlefunction fiber optic cable. The spectral information, after passingthrough the sample, was collected using OCEAN OPTICS Drivers inconjunction with propriety software from Transitions Optical, Ltd. Whilethe photochromic material was activated, the position of the polarizerwas rotated back and forth to polarize the light from the monitoringlight source to the 90° polarization plane and back. Data was collectedfor approximately 600 to 1200 seconds at 5 second intervals duringactivation. For each test, rotation of the polarizers was adjusted tocollect data in the following sequence of polarization planes: 0°, 90°,90°, 0°, etc.

Absorption ratio (AR) is the ratio of absorbance measured at 90°polarization (perpendicular orientation with the analyzer polarizer,minimum transmission) and 0° polarization (parallel orientation with theanalyzer polarizer, maximum transmission).

Change in optical density (ΔOD) from the bleached state (unactivatedstate) to the darkened state (activated state) was determined byestablishing the initial transmittance, opening the shutter from thexenon lamp to provide ultraviolet radiation to change the test specimenfrom the bleached state to an activated state. Data was collected atselected intervals of time, measuring the transmittance in the activatedstate, and calculating the change in optical density according to theformula: ΔOD=log(% Tb/%Ta), where % Tb is the percent transmittance inthe bleached state, %Ta is the percent transmittance in the activatedstate and the logarithm is to the base 10.

The fade half-life (T½) is the time interval in seconds for the ΔOD ofthe activatedj form of the photochromic compounds in the test specimensto reach one half the ΔOD measured after fifteen minutes, or aftersaturation or near-saturation was achieved, at room temperature afterremoval of the source of activating light, e.g., by closing the shutter.

The photochromic performance test results (absorption ratio and fadehalf-life)

obtained from the Examples according to the present invention andComparative Examples (CE) are summarized in the following Table 10.

TABLE 10 Photochromic Performance Test Results Example AR Fade (T_(1/2))Example 45 6.9 198 Example 46 6.5 188 Example 47 7.4 186 Example 48 7.3195 Example 49 6.6 202 Example 50 5.8 280 Example 51 5.6 196 Example 525.3 182 Example 53 5.6 205 Example 54 5.6 201 CE-55 4.8 244 CE-56 4.8237 CE-57 4.7 239

The results summarized in Table 10 above demonstrate that a coatinglayer including a mesogen-containing compound according to the presentinvention provides improved dichroic properties in the activated state(as indicated by AR values of greater magnitude), as compared to: thecomparative examples which do not include a mesogen-containing compoundhaving a terminal R-substituted dicyclohexyl group (CE-55 and CE-56);and the comparative example that does not include a mesogen-containingcompound (CE-57). Improved dichroic properties were observed withmesogen-containing compounds according to the present invention having:two terminal R-substituted dicyclohexyl groups (Examples 45-50); and asingle terminal R-substituted dicyclohexyl group and a single terminalacrylate group (Examples 51-54). In addition, mesogen-containingcompounds according to the present invention were observed to provideimproved fade half-life values (Examples 45-49 and Examples 51-54) ascompared to Comparative Examples CE-55, CE-56, and CE-57.

The present invention has been described with reference to specificdetails of particular embodiments thereof. It is not intended that suchdetails be regarded as limitations upon the scope of the inventionexcept insofar as to the extent that they are included in theaccompanying claims.

1. A mesogen-containing compound represented by the following Formula(I),

wherein: (A) Mesogen-1 is represented by the following Formula (II),

wherein: R is selected from hydrogen, and alkyl, and e′ and f′ for eachoccurrence for Formula (II) are independently from 0 to 2, provided thesum of e′ and f′ is at least 2; (B) Mesogen-2 is represented by Formula(II) of Mesogen-1, or the following Formula (III),

wherein: P is selected from R, acrylate, methacrylate, oxirane, andhydroxyl; d is 0 to 10; S₁ independently for each d is selected from anS₁-spacer unit chosen from —(CH₂)—-; and —O—; Qi is a divalent groupselected from the group consisting of unsubstituted or substituted aryl;wherein the aryl substituents, are each independently selected fromalkyl and halogen; and e″ and f″ for each occurrence for Formula (III)are independently from 0 to 4, provided the sum of e″ and f″ is from 2to 4; wherein independently for each of Formula (II) and Formula (III),(i) Q₂ and Q₃ for each occurrence are independently a divalent groupselected from the group consisting of unsubstituted or substitutedcycloalkyl group; unsubstituted or substituted aryl; wherein thecycloalkyl group substituents, aryl substituents, are each independentlyselected from alkyl and halogen; (ii) S₂, S₃, and S₄ for each occurrenceare independently selected from a spacer unit chosen from —(CH₂)—; —O—;and —C(O) ; and (iii) e, f, and g for each occurrence are independently0 to 2, provided that when two spacer units comprising heteroatoms arelinked together the spacer units are linked so that heteroatoms are notdirectly linked to each other; (C) -L- is represented by the followingFormula (IV),-(A-B)_(y)-E0  (IV) wherein: (i) y is 1 to 30; (ii) each A independentlyfor each y is a divalent group selected from the group consisting ofaliphatic group and haloaliphatic group; (iii) each B independently foreach y is a divalent group selected from the group consisting of —O—;—C(O)O—; —Si(R₄)(R₄)- where each R₄ is independently selected frommethyl, ethyl, and phenyl; unsubstituted or substituted aryl; andunsubstituted or substituted —O—(Aryl)—O—; wherein the arylsubstituents, and —O—(Aryl)—O- substituents are each independentlyselected from alkyl; and (iv) E is a divalent group selected from thegroup consisting of aliphatic group.
 2. The mesogen-containing compoundof claim 1, wherein: (B) for Formula (III), Q₁ is a divalent groupselected from the group consisting of unsubstituted or substitutedphenyl; wherein the phenyl substituents, are each independently selectedfrom alkyl and halogen; and wherein independently for each of Formula(II) and Formula (III), Q₂ and Q₃ for each occurrence are independentlya divalent group selected from the group consisting of unsubstituted orsubstituted phenyl; wherein the phenyl substituents, are eachindependently selected from alkyl and halogen.
 3. The mesogen-containingcompound of claim 2, wherein: for Formula (III), Q₁ is a divalent groupselected from the group consisting of unsubstituted or substituted1,4-phenyl; wherein the 1,4-phenyl substituents, are each independentlyselected from alkyl and halogen; and independently for each of Formula(II) and Formula (III), Q₂ and Q₃ for each occurrence are independentlya divalent group selected from the group consisting of unsubstituted orsubstituted 1,4-phenyl; wherein the 1,4 cycloalkyl substituents, areeach independently selected from alkyl and halogen.
 4. Themesogen-containing compound of claim 3, wherein: (A) for Formula (II), Ris selected from hydrogen and alkyl; (B) for Formula (III), P isselected from R, acrylate, and methacrylate; (C) for Formula (IV), (ii)each A independently for each y is a divalent group selected from thegroup consisting of alkyl; (iii) each B independently for each y is adivalent group selected from the group consisting of —O—; —C(O)O—;unsubstituted or substituted phenyl; and unsubstituted or substituted—O—(Phenyl)—O—; wherein the phenyl substituents, and —O—(Phenyl)—O-substituents are each independently selected from alkyl; and (iv) E is adivalent group selected from the group consisting of alkyl groups. 5.The mesogen-containing compound of claim 1, wherein provided that forFormula (IV), no B or only one B is a divalent group selected from thegroup consisting of unsubstituted or substituted aryl; and unsubstitutedor substituted —O—(Aryl)—O—.
 6. The mesogen-containing compound of claim5, wherein provided that for Formula (IV), no B or only one B is adivalent group selected from the group consisting of unsubstituted orsubstituted phenyl; and unsubstituted or substituted —O—(Phenyl)—O—. 7.The mesogen-containing compound of claim 1, wherein Mesogen-2 isrepresented by Formula (II) of Mesogen-1.
 8. The mesogen-containingcompound of claim 7, wherein Mesogen-1 and Mesogen-2 are the same. 9.The mesogen-containing compound of claim 1, wherein -L- comprises atleast 20 bonds.
 10. A liquid crystal composition comprising themesogen-containing compound of claim
 1. 11. The liquid crystalcomposition of claim 10, further comprising at least one of aphotochromic compound, a dichroic compound, and a photochromic-dichroiccompound.
 12. The liquid crystal composition of claim 11, wherein saidphotochromic-dichroic compound comprises at least one photochromicmoiety, and said photochromic compound and each photochromic moiety ofsaid photochromic-dichroic compound are in each case independentlyselected from indeno-fused naphthopyrans, naphtho[1,2-b]pyrans,naphtho[2,1-b]pyrans, spirofluoroeno[1,2-b]pyrans, phenanthropyrans,quinolinopyrans, fluoroanthenopyrans, spiropyrans, benzoxazines,naphthoxazines, spiro(indoline)naphthoxazines,spiro(indoline)pyridobenzoxazines, spiro(indoline)fluoranthenoxazines,spiro(indoline)quinoxazines, fulgides, fulgimides, diarylethenes,diarylalkylethenes, diarylalkenylethenes, non-thermally reversiblephotochromic compounds, and mixtures thereof.
 13. An optical elementcomprising: a substrate; and a layer on at least a portion of a surfaceof said substrate, wherein said layer comprises the mesogen-containingcompound of claim 1.